Fluorene derivative, light-emitting elements, light-emitting device, electronic device, and lighting device

ABSTRACT

In the formula, R1 to R8 independently represent any of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group. Further, α1 to α4 independently represent any of a substituted or unsubstituted arylene group having 6 to 12 carbon atoms. Furthermore, Ar1 and Ar2 independently represent any of an aryl group having 6 to 13 carbon atoms in a ring and Ar3 represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. J, k, m, and n each independently represent 0 or 1.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.14/730,407, filed Jun. 4, 2015, now allowed, which is a continuation ofU.S. application Ser. No. 12/786,997, filed May 25, 2010, now U.S. Pat.No. 9,051,239, which claims the benefit of foreign a priorityapplication filed in Japan as Serial No. 2009-131504 on May 29, 2009,all of which are incorporated by reference.

TECHNICAL FIELD

The present invention relates to a fluorene derivative, a light-emittingelement, a light-emitting device, an electronic device, and a lightingdevice.

BACKGROUND ART

In recent years, research and development have been extensivelyconducted on light-emitting elements using electroluminescence. In abasic structure of such a light-emitting element, a layer containing asubstance with a light-emitting property is interposed between a pair ofelectrodes. By voltage application to this element, light emission canbe obtained from the substance having a light-emitting property.

Since such a light-emitting element is of self-light-emitting type, itis considered that the light-emitting element has advantages over aliquid crystal display in that visibility of pixels is high, backlightis not required, and so on and is therefore suitable as flat paneldisplay elements. Besides, such a light-emitting element has advantagesin that it can be formed to be thin and lightweight, and has quite fastresponse speed.

Furthermore, since such a light-emitting element can be formed in a filmform, planar light emission can be easily obtained. Thus, a large-areaelement utilizing planar light emission can be formed. This is a featurewhich is difficult to be obtained by point light sources typified by anincandescent lamp and an LED or linear light sources typified by afluorescent lamp. Accordingly, the light-emitting element is extremelyeffective for use as a surface light source applicable to lighting andthe like.

Light-emitting elements utilizing electroluminescence are broadlyclassified according to whether they use an organic compound or aninorganic compound as a light-emitting substance. When an organiccompound is used as a light-emitting substance, by voltage applicationto a light-emitting element, electrons and boles are injected into alayer including the light-emitting organic compound from a pair ofelectrodes, whereby current flows. Light is emitted when the carriers(electrons and holes) are recombined and the electrons and holes of theorganic compound returns to the ground state from the excited statewhere both the electrons and the holes are generated in organicmolecules with a light-emitting property.

Because of such a mechanism, the light-emitting element is called acurrent-excitation light-emitting element. It is to be noted that theexcited state generated by an organic compound can be a singlet excitedstate or a triplet excited state, and luminescence from the singletexcited state is referred to as fluorescence, and luminescence from thetriplet excited state is referred to as phosphorescence.

In addition to light emission by recombination of current excitationcarriers, which is described above, there is a method in whichexcitation energy is transferred to another organic compound, wherebythe organic compound is excited to provide light emission. This is anelement structure in which a light-emitting material is diffused (doped)to the light-emitting layer in general organic EL. A host means amaterial into which a light-emitting material is diffused and a dopantmeans a material which is diffused into the host. This, in order tosolve a problem in that organic molecules to provide light emission havelow light emission efficiency because stacking interaction occurs whenthey are high concentration (concentration quenching), contributes tohigher light emission efficiency by doping the organic molecules to thehost and suppressing stack. At this time, the excitation energy bycurrent excitation is transferred to the dopant from the host excited bycurrent excitation, so that the dopant emits light.

This excitation energy transfer occurs only when transfer from highexcitation energy to low excitation energy is performed. Therefore, amaterial having a high excitation state is preferably used for a hostmaterial.

An organic EL layer has a plurality of layers, and a carrier-transportlayer is generally provided between a light-emitting layer and anelectrode. As one of the reasons, a carrier-transport layer can preventexcitation energy in the light-emitting layer from quenching caused byenergy transfer to the electrode. Further, a material (anexciton-blocking material) having higher excitation energy than alight-emitting layer is preferably used for a carrier-transport layerwhich is adjacent to the light-emitting layer so that excitation energyin the light-emitting layer is not transferred.

As another reason to provide a carrier-injection layer and acarrier-transport layer between a light-emitting layer and an electrodein an organic EL, it is to adjust a carrier injection partition betweenadjacent layers. Accordingly, recombination can be efficiently performedin the light-emitting layer.

In improving element characteristics of such a light-emitting element,there are a lot of problems which depend on a substance, and in order tosolve the problems, improvement of an element structure, development ofa substance, and the like have been carried out (for example, see PatentDocument 1).

REFERENCE Patent Document

[Patent Document 1]: PCT International Publication No. 08/062636

DISCLOSURE OF INVENTION

An object of an embodiment of the present invention is to provide anovel fluorene derivative as a substance having a high hole-transportproperty. Another object is to provide a light-emitting element havinghigh light emission efficiency by application of the novel fluorenederivative for a light-emitting element. Another object of an embodimentof the present invention is to provide a light-emitting device, anelectronic device, and a lighting device each with low power consumptionand low driving voltage.

An embodiment of the present invention is a fluorene derivativerepresented by General Formula (G1) below.

In the formula, R¹ to R⁸ independently represent any of a hydrogen atom,an alkyl group having 1 to 6 carbon atoms, a substituted orunsubstituted phenyl group, or a substituted or unsubstituted biphenylgroup. Further, α¹ to α⁴ independently represent any of a substituted orunsubstituted arylene group having 6 to 12 carbon atoms. Furthermore,Ar¹ and Ar² independently represent any of an aryl group having 6 to 13carbon atoms in a ring and Ar³ represents an alkyl group having 1 to 6carbon atoms or a substituted or unsubstituted aryl group having 6 to 12carbon atoms. J, k, m, and n independently represent 0 or 1. Note thatat least one of J and k is 1.

In the above structure, R¹ to R⁸ in General Formula (G1) areindependently represented by any of Structural Formula (R-1) toStructural Formula (R-9).

In the above structure, α¹ to α⁴ in General Formula (G1) areindependently represented by any of Structural Formula (α-1) toStructural Formula (α-3).

In the above structure, Ar¹ and Ar² in General Formula (G1) areindependently represented by any of Structural Formula (Ar-1) toStructural Formula (Ar-6), and Ar³ is represented by any of StructuralFormula (Ar3-1) to Structural Formula (Ar3-8).

Another embodiment of the present invention is represented by StructuralFormula (101), Structural Formula (151), or Structural Formula (118)below.

Further, another embodiment of the present invention is a light-emittingelement including an EL layer between a pair of electrodes. The EL layerincludes at least a light-emitting layer and a hole-transport layer andthe hole-transport layer includes one or a plurality of the fluorenederivatives described above.

Furthermore, another embodiment of the present invention is alight-emitting device formed using the above-described light-emittingelement. Another embodiment of the present invention is an electronicdevice formed using the above-described light-emitting device. Anotherembodiment of the present invention is a lighting device formed usingthe above-described light-emitting device

The light-emitting device of an embodiment of the present invention is alight-emitting device including the aforementioned light-emittingelement and a control means which controls the light emission from thelight-emitting element. Note that the light-emitting device in thisspecification includes image display devices, light-emitting devices, orlight sources (including lighting device). In addition, thelight-emitting device includes any of the following modules in itscategory: a module in which a connector such as an flexible printedcircuit (FPC), a tape automated bonding (TAB) tape, or a tape carrierpackage (TCP) is attached to a panel; a module having a TAB tape or aTCP provided with a printed wiring board at the end thereof; and amodule having an integrated circuit (IC) directly mounted on alight-emitting element by a chip on glass (COG) method.

Further, an electronic device of an embodiment of the light-emittingdevice of the present invention is used for a display portion is alsoincluded in the category of the present invention. Consequently, anembodiment of an electronic device of the present invention includes adisplay portion, in which the display portion is provided with the abovelight-emitting device.

Furthermore, a lighting device using an embodiment of the light-emittingdevice of the present invention is also included in the category of thepresent invention. Therefore, an embodiment of the lighting device ofthe present invention is provided with the above light-emitting device.

Since the fluorene derivative of the present invention has a highhole-transport property, it can be mainly used for a hole-transportlayer which is included in an EL layer of a light-emitting element. Inaddition, the fluorene derivative of the present invention is used forthe hole-transport layer to form a light-emitting element, whereby alight-emitting element having high luminous efficiency can be formed.

Also, by use of such a light-emitting element, a light-emitting device,an electronic device, and a lighting device with low power consumptionand low drive voltage can be obtained.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1A and 1B are views each illustrating a light-emitting element;

FIGS. 2A to 2C are views each illustrating a light-emitting element;

FIGS. 3A and 3B are views each illustrating a light-emitting element;

FIGS. 4A and 4B are views illustrating a light-emitting device;

FIGS. 5A and 5B are views illustrating a light-emitting device;

FIGS. 6A to 6D are views illustrating electronic devices;

FIG. 7 is a view illustrating an electronic device;

FIG. 8 is a view illustrating a lighting device;

FIG. 9 is a view illustrating a lighting device;

FIGS. 10A and 10B are ¹H-NMR charts of4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine;

FIG. 11 is a graph showing absorption spectra of4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine;

FIG. 12 is a graph showing emission spectra of4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine;

FIG. 13 is a graph showing a result of CV measurement of4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine;

FIGS. 14A and 14B are ¹H-NMR charts of4-phenyl-4′-[4-(9-phenylfluoren-9-yl)phenyl]triphenylamine;

FIG. 15 is a graph showing absorption spectra of4-phenyl-4′-[4-(9-phenylfluoren-9-yl)phenyl]triphenylamine;

FIG. 16 is a graph showing emission spectra of4-phenyl-4′-[4-(9-phenylfluoren-9-yl)phenyl]triphenylamine;

FIG. 17 is a graph showing a result of CV measurement of4-phenyl-4′-[4-(9-phenylfluoren-9-yl)phenyl]triphenylamine;

FIG. 18 is a view illustrating a light-emitting element of Examples;

FIG. 19 is a graph showing current density vs. luminance characteristicsof Comparative Light-Emitting Element 1 and Light-Emitting Element 2;

FIG. 20 is a graph showing voltage vs. luminance characteristics ofComparative Light-Emitting Element 1 and Light-Emitting Element 2;

FIG. 21 is a graph showing luminance vs. current efficiencycharacteristics of Comparative Light-Emitting Element 1 andLight-Emitting Element 2;

FIG. 22 is a graph showing current density vs. luminance characteristicsof Light-Emitting Element 3;

FIG. 23 is a graph showing voltage vs. luminance characteristics ofLight-Emitting Element 3;

FIG. 24 is a graph showing luminance vs. current efficiencycharacteristics of Light-Emitting Element 3;

FIG. 25 is a graph showing results of a reliability test ofLight-Emitting Element 3;

FIG. 26 is a graph showing current density vs. luminance characteristicsof Light-Emitting Element 4 and Light-Emitting Element 5;

FIG. 27 is a graph showing voltage vs. luminance characteristics ofLight-Emitting Element 4 and Light-Emitting Element 5;

FIG. 28 is a graph showing luminance vs. current efficiencycharacteristics of Light-Emitting Element 4 and Light-Emitting Element5;

FIG. 29 is a graph showing results of a reliability test ofLight-Emitting Element 4 and Light-Emitting Element 5;

FIG. 30 is a graph showing current density vs. luminance characteristicsof Light-Emitting Element 6 and Comparative Light-Emitting Element 7;

FIG. 31 is a graph showing voltage vs. luminance characteristics ofLight-Emitting Element 6 and Comparative Light-Emitting Element 7;

FIG. 32 is a graph showing luminance vs. current efficiencycharacteristics of Light-Emitting Element 6 and ComparativeLight-Emitting Element 7;

FIG. 33 is a graph showing emission spectra of Light-Emitting Element 6and Comparative Light-Emitting Element 7;

FIG. 34 is a graph showing current density vs. luminance characteristicsof Light-Emitting Element 8 to Light-Emitting Element 10;

FIG. 35 is a graph showing voltage vs. luminance characteristics ofLight-Emitting Element 8 to Light-Emitting Element 10;

FIG. 36 is a graph showing luminance vs. current efficiencycharacteristics of Light-Emitting Element 8 to Light-Emitting Element10;

FIG. 37 is a graph showing results of a reliability test ofLight-Emitting Element 8 to Light-Emitting Element 10.

FIG. 38 is a graph showing current density vs. luminance characteristicsof Light-Emitting Element 11 and comparative Light-Emitting Element 12;

FIG. 39 is a graph showing voltage vs. luminance characteristics ofLight-Emitting Element 11 and comparative Light-Emitting Element 12;

FIG. 40 is a graph showing luminance vs. current efficiencycharacteristics of Light-Emitting Element 11 and comparativeLight-Emitting Element 12;

FIG. 41 is a graph showing emission spectra of Light-Emitting Element 11and comparative Light-Emitting Element 12;

FIG. 42 is a graph showing current density vs. luminance characteristicsof Light-Emitting Element 13;

FIG. 43 is a graph showing voltage vs. luminance characteristics ofLight-Emitting Element 13;

FIG. 44 is a graph showing luminance vs. current efficiencycharacteristics of Light-Emitting Element 13;

FIGS. 45A and 45B are ¹H-NMR charts of4-phenyl-3′-(9-phenylfluoren-9-yl)triphenylamine;

FIG. 46 is a graph showing absorption spectra of4-phenyl-3′-(9-phenylfluoren-9-yl)triphenylamine;

FIG. 47 is a graph showing emission spectra of4-phenyl-3′-(9-phenylfluoren-9-yl)triphenylamine;

FIG. 48 is a graph showing current density vs. luminance characteristicsof Light-Emitting Element 14 and Comparative Light-Emitting Element 15;

FIG. 49 is a graph showing voltage vs. luminance characteristics ofLight-Emitting Element 14 and Comparative Light-Emitting Element 15;

FIG. 50 is a graph showing luminance vs. current efficiencycharacteristics of Light-Emitting Element 14 and ComparativeLight-Emitting Element 15;

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, Embodiments of the present invention are described withreference to the drawings. Note that the invention is not limited to thefollowing description, and it will be easily understood by those skilledin the art that various changes and modifications can be made withoutdeparting from the spirit and scope of the invention. Therefore, theinvention should not be construed as being limited to the description inthe following embodiments.

(Embodiment 1)

In Embodiment 1, a fluorene derivative of an embodiment of the presentinvention is described.

The fluorene derivative of an embodiment of the present invention is afluorene derivative represented by General Formula (G1).

In the formula, R¹ to R⁸ independently represent any of a hydrogen atom,an alkyl group having 1 to 6 carbon atoms, a substituted orunsubstituted phenyl group, or a substituted or unsubstituted biphenylgroup. Further, α¹ to α⁴ independently represent any of a substituted orunsubstituted arylene group having 6 to 12 carbon atoms. Furthermore,Ar¹ and Ar² independently represent any of an aryl group having 6 to 13carbon atoms in a ring and Ar³ represents an alkyl group having 1 to 6carbon atoms or a substituted or unsubstituted aryl group having 6 to 12carbon atoms. J, k, m, and n are independently represent 0 or 1. Notethat at least one of J and k is 1.

In the case where R¹ to R⁸, α¹ to α⁴, Ar¹, Ar², Ar³ have substituents,an alkyl group such as a methyl group, an ethyl group, a propyl group, apentyl group or a hexyl group, or an aryl group such as a phenyl groupor a biphenyl group can be given as an example of the substituent.Alternatively, the substituents may be connected to each other to form aring (for example, a biphenyl group forms a ring with a fluorenyl groupof Ar¹ or Ar² to be a 9,9′-spirofluorenyl group or a hexyl group forms aring to be a cyclohexyl group).

It is considered that when an alkyl group is used in General Formula(G1), the solubility in an organic solvent is improved; therefore, in acase where an element is formed using this material by a wet method, ause of a material having an alkyl group makes manufacturing an elementeasy, which is preferable.

As R¹ to R⁸ in General Formula (G1), a hydrogen atom, an alkyl groupsuch as a methyl group, an ethyl group, a propyl group, a pentyl groupor a hexyl group, a substituted or unsubstituted phenyl group, or asubstituted or unsubstituted aryl group such as a biphenyl group can begiven. Structural Formulae (R-1) to (R-9) are specifically given.

As α¹ to α⁴ in General Formula (G1), a substituted or unsubstitutedphenylene group can be given. Structural Formulae (α-1) to (α-3) arespecifically given.

As Ar¹ and Ar² in General Formula (G1), a substituted or unsubstitutedphenyl group, a substituted or unsubstituted biphenyl group, asubstituted or unsubstituted naphthyl group, a substituted orunsubstituted fluorenyl group, or a substituted or unsubstituted arylgroup such as spirofluorenyl group can be given. Structural Formulae(Ar-1) to (Ar-6) are specifically given. (Ar-4) below is one in which abiphenyl group forms a ring with a fluorenyl group of Ar¹ or Ar² to be a9,9′-spirofluorenyl group.

In this case, when a condensed ring group is used as in (Ar-2) or(Ar-3), a carrier-transport property is improved, which is preferable.Also in this case, when α¹ or α² which is between a condensed ring groupand a nitrogen atom is 1, a band gap (Bg) of a molecule can be keptwider, which is preferable. Further, as in (Ar-5), a structure using abond binding by a sigma bond hardly makes conjugation from a nitrogenatom extend, and Bg and T1 level are high. Therefore, it is thought thatthis material can be used, in a light-emitting element with a shorterwavelength, as a material of a layer adjacent to the light-emittinglayer or a dopant material to the light-emitting layer, which ispreferable. Further, when a condensed ring group having large and rigidmolecular weight, such as (Ar-2), (Ar-3), or (Ar-4), is used,thermophysical properties such as the glass transition point (T_(g)) areimproved, which is preferable.

As Ar³ in General Formula (G1), an alkyl group such as a methyl group,an ethyl group, a propyl group, a pentyl group or a hexyl group, asubstituted or unsubstituted phenyl group, or a substituted orunsubstituted aryl group such as a biphenyl group can be given.Structural Formulae (Ar3-1) to (Ar3-8) are specifically given.

As specific examples of a fluorene derivative represented by GeneralFormula (G1), fluoren derivatives represented by Structural Formulae(100) to (123) or Structural Formulae (150) to (173) can be given.However, an embodiment of the present invention is not limited to these.

A variety of reactions can be applied to a synthesis method of afluorene derivative of an embodiment of the present invention. Forexample, the fluorene derivative represented by General Formula (G1) ofan embodiment of the present invention can be synthesized by synthesisreactions described below. Note that the synthesis method of thefluorene derivative of an embodiment of the present invention is notlimited to the following synthesis methods.

<Synthesis Method 1 of the Fluorene Derivative Represented by GeneralFormula (G1)>

As shown in a scheme (A-1), a 1-halogenated biphenyl derivative (a1) islithiated or made into a Grignard reagent and is reacted with a benzoylderivative (a2) to be dehydroxilated, so that a haloarylfluorenederivative (a3) can be obtained.

An aryl compound including a halogen group in the scheme (A-1) isactivated, is reacted with a benzoyl derivative to be a phenolderivative, and is dehydroxilated by addition of acid, whereby afluorene derivative can be obtained.

As an example of the activation, a reaction using alkyl lithium reagentto perform lithiation or a reaction using activated magnesium to obtaina Grignard reagent can be used. As alkyl lithium, n-butyllithium,tert-butyllithium, methyllithium, and the like can be given. As acid,hydrochloric acid or the like can be used. As a dehydrating solvent, anether such as diethyl ether or tetrahydrofuran (THF) can be used.

As shown in a scheme (A-2), a halogenated arene derivative (a4) and anarylamine derivative (a5) are coupled, whereby a diarylamine derivative(a6) can be obtained.

As shown in a scheme (A-3), a haloarylfluorene derivative (a3) and adiarylamine derivative (a6) are coupled, whereby the fluorene derivativerepresented by the above General Formula (G1) can be obtained.

Note that X¹, X², or X³ in the above schemes (A-1) to (A-3) representshalogen and preferably represents bromine or iodine, more preferablyrepresents iodine because of high reaction.

In the schemes (A-2) and (A-3), a coupling reaction of an aryl compoundincluding a halogen group and an aryl compound including amine (aprimary arylamine compound or a secondary azylamine compound) has avariety of reaction conditions. As an example, a synthesis method usinga metal catalyst in the presence of a base can be employed.

The case where a Buchwald-Hartwig reaction is performed in the schemes(A-2) and (A-3) is shown. A palladium catalyst can be used for the metalcatalyst and a mixture of a palladium complex and a ligand thereof canbe used for the palladium catalyst. As examples of the palladiumcatalyst, bis(dibenzylideneacetone)palladium(0), palladium(II) acetate,and the like can be given. As the ligand, tri(tert-butyl)phosphine,tri(n-hexyl)phosphine, tricyclohexylphosphine,1,1-bis(diphenylphosphino)ferrocene (abbreviation: DPPF), and the likecan be given. As a substance which can be used as the base, an organicbase such as sodium tert-butoxide, an inorganic base such as potassiumcarbonate, and the like can be given. In addition, the above reaction ispreferably performed in a solution, and toluene, xylene, benzene, andthe like can be given as a solvent that can be used in the abovereaction. However, the catalyst, ligand, base, and solvent which can beused are not limited thereto. In addition, the reaction is preferablyperformed under an inert atmosphere of nitrogen, argon, or the like.

The case where an Ullmann reaction is performed in the schemes (A-2) and(A-3) is shown. A copper catalyst can be used as the metal catalyst, andcopper iodide (I) and copper acetate (II) can be given as the coppercatalyst. As an example of a substance that can be used as the base, aninorganic base such as potassium carbonate can be given. The abovereaction is preferably performed in a solution, and1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (abbreviation: DMPU),toluene, xylene, benzene, and the like can be given as a solvent thatcan be used in the above reaction. However, the catalyst, ligand, base,and solvent which can be used are not limited thereto. In addition, thereaction is preferably performed under an inert atmosphere of nitrogen,argon, or the like.

Note that a solvent having a high boiling point such as DMPU or xyleneis preferably used because, by an Ullmann reaction, an object can beobtained in a shorter time and at a higher yield when the reactiontemperature is higher than or equal to 100° C. In particular, DMPU ismore preferable because the reaction temperature is more preferablyhigher than or equal to 150° C.

<Synthesis Method 2 of the Fluorene Derivative Represented by GeneralFormula (G1)>

For example, as shown in a scheme (B-1), the haloarylfluorene derivative(a3) and the arylamine derivative (a5) are coupled, whereby adiarylamine derivative having a fluorenyl group (b1) can be obtained.

As shown in a scheme (B-2), the diarylamine derivative having afluorenyl group (b1) and the halogenated arene derivative (a4) arecoupled, whereby the fluorene derivative represented by the aboveGeneral Formula (G1) can be obtained.

Note that X² and X³ in the above schemes (B-1) and (B-2) representhalogen and preferably represent bromine or iodine, more preferablyrepresent iodine because of high reaction.

In the schemes (B-1) and (B-2), a coupling reaction of an aryl compoundincluding a halogen group and an aryl compound including amine (aprimary arylamine compound or a secondary arylamine compound) has avariety of reaction conditions. As an example, a synthesis method usinga metal catalyst in the presence of a base can be employed.

The Buchwald-Hartwig reaction or the Ullmann reaction can be employed inthe schemes (B-1) and (B-2) in a manner similar to the schemes (A-2) and(A-3).

<Synthesis Method 3 of the Fluorene Derivative Represented by GeneralFormula (G1)>

For example, as shown in a scheme (C-1), a halogenated arylfluorenederivative (c1) is lithiated or made into a Grignard reagent and isreacted with an organoboronic acid, whereby an arylboronic acidderivative having a fluorenyl group (c2) can be obtained (Note that Jrepresents 1.).

As shown in a scheme (C-2), a triarylamine derivative (c3) ishalogenated, whereby a halogenated triarylamine derivative (c4) can beobtained.

As shown in a scheme (C-3), the arylboronic acid derivative having afluorenyl group (c2) and the halogenated triarylamine derivative (c4)are coupled, whereby the fluorene derivative represented by the aboveGeneral Formula (G1) can be obtained.

Note that k in the schemes (C-2) and (C-3) represents 1.

X⁴ and X⁵ in the above schemes (C-1) to (C-3) represent halogen andpreferably represent bromine or iodine, more preferably represent iodinebecause of high reaction.

A reaction in the scheme (C-1) in which an aryl compound including ahalogen group is used to obtain an aryl compound including a boronicacid group (or an organoboron group) has a variety of reactionconditions. R¹ to R⁸ in the scheme represent hydrogen or an alkyl group.

As an example of the reaction, after an aryl compound including ahalogen group is lithiated using an alkyllithium reagent, boronoxidation or organoboration of the aryl compound including a halogengroup is performed adding a boron reagent. As the alkyllithium reagent,n-butyllithium, methyllithium, or the like can be used. As the boronreagent, Trimethyl borate, isopropyl borate, or the like can be used. Asa dehydrating solvent, an ether such as diethyl ether or tetrahydrofuran(THF) can be used. Alternatively, a Grignard reagent with activatedmagnesium can be used instead of a lithiated reagent.

A halogenated reaction in the scheme (C-2) has a variety of reactionconditions. For example, a reaction in which a halogenating agent canused in the presence of a polar solvent can be used. As the halogenatingagent, N-Bromosuccinimide (abbreviation: NBS), N-Iodosuccinimide(abbreviation: NIS), bromine, iodine, potassium iodide, or the like canbe used. As the halogenating agent, the use of a bromide is preferablebecause synthesis can be performed at low cost. It is preferable to usean iodide as a halogenating agent because the reaction proceeds moreeasily in the case where a reaction using the generated object as asource is performed next (a portion which is replaced by iodine has ahigher activation). Note that k in the scheme (C-2) represents 1 andhalogenation peculiarly occurs at a para position with respect to amine.

A coupling reaction of an aryl compound including a halogen group and anaryl compound including a boronic acid (arylboronic acid) in the scheme(C-3) has a variety of reaction conditions. As an example thereof, asynthesis method using a metal catalyst in the presence of a base can beemployed.

In the scheme (C-3), the case of using a Suzuki-Miyaura reaction isdescribed. As the metal catalyst, a palladium catalyst such as a mixtureof a palladium complex and the ligand thereof can be used. As thepalladium catalyst, palladium(II) acetate,tetrakis(triphenylphosphine)palladium(0),bis(triphenylphosphine)palladium(II)dichloride, and the like can begiven. As the ligand, tri(ortho-tolyl)phosphine, triphenylphosphine,tricyclohexylphosphine, and the like can be given. In addition, as thebase, an organic base such as sodium tert-butoxide, an inorganic basesuch as potassium carbonate, and the like can be given. The reaction ispreferably performed in a solution, and as the solvent which can beused, a mixed solvent of toluene and water, a mixed solvent of toluene,an alcohol such as ethanol, and water, a mixed solvent of xylene andwater, a mixed solvent of xylene, an alcohol such as ethanol, and water;a mixed solvent of benzene and water; a mixed solvent of benzene, analcohol such as ethanol, and water, a mixed solvent of ethers such asethyleneglycoldimethylether and water, and the like can be given.However, the catalyst, ligand, base, and solvent which can be used arenot limited thereto. Alternatively, in the scheme, an organoboroncompound of an aryl derivative, aryl aluminum, aryl zirconium, arylzinc, aryl tin compound, or the like may be used instead of anarylboronic acid. In addition, the reaction is preferably performedunder an inert atmosphere of nitrogen, argon, or the like.

(Embodiment 2)

In Embodiment 2, a light-emitting element which is formed using, for ahole-transport layer, the fluorene derivative of an embodiment of thepresent invention described in Embodiment 1 is described.

The light-emitting element in Embodiment 2 includes a first electrodewhich functions as an anode, a second electrode which functions as acathode, and an EL layer interposed between the first electrode and thesecond electrode. Note that the light-emitting element in Embodiment 2can exhibit light emission when voltage is applied to each electrode sothat the potential of the first electrode is higher than that of thesecond electrode.

In addition, the EL layer of the light-emitting element in Embodiment 2includes a first layer (hole-injection layer), a second layer(hole-transport layer), a third layer (light-emitting layer), a fourthlayer (electron-transport layer), and a fifth layer (electron-injectionlayer), from the first electrode side.

A structure of the light-emitting element in Embodiment 2 is describedusing FIGS. 1A and 1B. A substrate 101 is used as a support of thelight-emitting element. For the substrate 101, glass, quartz, plastics,or the like can be used, for example.

Note that although the above substrate 101 may remain in alight-emitting device or an electronic device which is a productutilizing the light-emitting element of an embodiment of the presentinvention, the substrate 101 may only have a function as the support ofthe light-emitting element in the manufacturing process of thelight-emitting element, without remaining in an end product.

For the first electrode 102 formed over the substrate 101, a metal, analloy, an electrically conductive compound, a mixture thereof, or thelike which has a high work function (specifically, a work function of4.0 eV or more) is preferably used. Specific examples are given below:indium tin oxide (ITO), indium tin oxide containing silicon or siliconoxide, indium zinc oxide (IZO), and indium oxide containing tungstenoxide and zinc oxide. Besides, gold (Au), platinum (Pt), nickel (Ni),tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co),copper (Cu), palladium (Pd), titanium (Ti), nitride of metal materials(for example, titanium nitride), and the like can be given. Note that inthe present invention, since the first layer 111 in the EL layer 103which is formed in contact with the first electrode 102 includes acomposite material which facilitates hole injection regardless of thework function of the first electrode 102, any known material can be usedas long as the material can be used as an electrode material (e.g., ametal, an alloy, an electrically conductive compound, a mixture thereof,and an element belonging to Group 1 or Group 2 of the periodic table).

These materials are usually formed by a sputtering method. For example,a film of indium oxide-zinc oxide (IZO) can be formed by a sputteringmethod using a target in which 1 to 20 wt % zinc oxide is added toindium oxide; and a film of indium oxide containing tungsten oxide andzinc oxide can be formed by a sputtering method using a target in which0.5 to 5 wt % tungsten oxide and 0.1 to 1 wt % zinc oxide are added toindium oxide. Alternatively, a vacuum evaporation method, a coatingmethod, an inkjet method, a spin coating method, or the like may beused.

Further, in the EL layer 103 formed over the first electrode 102, when acomposite material described later is used as a material for the firstlayer 111 formed in contact with the first electrode 102, any of avariety of metals, alloys, electrically conductive compounds, and amixture thereof can be used as a substance used for the first electrode102 regardless of whether the work function is high or low. For example,aluminum (Al), silver (Ag), an alloy containing aluminum (AlSi), or thelike can also be used.

Alternatively, it is possible to use any of elements belonging to Group1 and 2 of the periodic table, that is, alkali metals such as lithium(Li) and cesium (Cs), alkaline earth metals such as magnesium (Mg),calcium (Ca), and strontium (Sr), alloys containing them (e.g., MgAg andAlLi), rare earth metals such as europium (Eu) and ytterbium (Yb),alloys containing them, and the like which are materials with a low workfunction.

Note that in the case where the first electrode 102 is formed using analkali metal, an alkaline earth metal, or an alloy thereof, a vacuumevaporation method or a sputtering method can be used. Furtheralternatively, in the case where a silver paste or the like is used, acoating method, an inkjet method, or the like can be used.

The EL layer 103 formed over the first electrode 102 can be formed usinga known material, and either a low molecular compound or a highmolecular compound can be used. Note that the substance forming the ELlayer 103 is not limited to an organic compound and may partiallyinclude an inorganic compound.

The EL layer 103 is formed by stacking an appropriate combination of ahole-injection layer that includes a substance having a highhole-injection property, a hole-transport layer that includes asubstance having a high hole-transport property, a light-emitting layerthat includes a light-emitting substance, an electron-transport layerthat includes a substance having a high electron-transport property, anelectron-injection layer that includes a substance having a highelectron-injection property, and the like.

Note that the EL layer 103 illustrated in FIG. 1A includes the firstlayer (hole-injection layer) 111, the second layer (hole-transportlayer) 112, the third layer (light-emitting layer) 113, the fourth layer(electron-transport layer) 114, and the fifth layer (electron-injectionlayer) 115 which are in that order stacked from the first electrode 102side.

The first layer 111 which is a hole-injection layer is a hole-injectionlayer that includes a substance having a high hole-injection property.As the substance having a high hole-injection property, molybdenumoxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide,chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silveroxide, tungsten oxide, manganese oxide, or the like can be used.Alternatively, as a low molecular organic compound, aphthalocyanine-based compound such as phthalocyanine (abbreviation:H₂Pc), copper(II) phthalocyanine (abbreviation: CuPc), or vanadylphthalocyanine (abbreviation: VOPc) can be used. Note that the fluorenederivative of an embodiment of the present invention which is describedin Embodiment 1 can also be used in a similar manner.

Further, as examples of low molecular organic compounds, there arearomatic amine compounds such as4,4′,4″-tris(N,N-diphenylamino)triphenylamine (abbreviation: TDATA),4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine(abbreviation: MTDATA),4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation:DPAB),4,4′-bis(N-{4-[N′-(3-methylphenyl)-N′-phenylamino]phenyl}-N-phenylamino)biphenyl(abbreviation: DNTPD),1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenylamino]benzene(abbreviation: DPA3B),3-[N-(9-phenylcarbazol-3-yl)-N-phenylamino]-9-phenylcarbazole(abbreviation: PCzPCA1),3,6-bis[N-(9-phenylcarbazol-3-yl)-N-phenylamino]-9-phenylcarbazole(abbreviation: PCzPCA2), and3-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)amino]-9-phenylcarbazole(abbreviation: PCzPCN1), and the like. Note that the fluorene derivativeof an embodiment of the present invention which is described inEmbodiment 1 can also be used in a similar manner.

Further alternatively, any of high molecular compounds (e.g., oligomers,dendrimers, or polymers) can be used. For example, there are highmolecular compounds such as poly(N-vinylcarbazole) (abbreviation: PVK),poly(4-vinyltriphenylamine) (abbreviation: PVTPA),poly[N-(4-{N′-[4-(4-diphenylamino)phenyl]-N′-phenylamino}phenyl)methacrylamide](abbreviation: PTPDMA), orpoly[N,N′-bis(4-butylphenyl)-N,N′-bis(bis(phenyl)benzidine](abbreviation: Poly-TPD). Alternatively, a high molecular compound towhich acid is added, such aspoly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid) (PEDOT/PSS),or polyaniline/poly(styrenesulfonic acid) (PAni/PSS), can be used.

Moreover, for the first layer 111, the composite material in which anacceptor substance is mixed into a substance having a highhole-transport property can be used. By using such a substance with ahigh hole-transport property containing an acceptor substance, amaterial used to form an electrode may be selected regardless of itswork function. In other words, besides a material with a high workfunction, a material with a low work function may also be used as thefirst electrode 102. Such a composite material can be formed byco-depositing a substance having a high hole-transport property and asubstance having an acceptor property. Note that in this specification,the word “composite” means not only a state in which two materials aresimply mixed but also a state in which a plurality of materials aremixed and charges are transferred between the materials.

As the organic compound for the composite material, a variety ofcompounds such as an aromatic amine compound, a carbazole derivative,aromatic hydrocarbon, and a high molecular compound (such as oligomer,dendrimer, or polymer) can be used. The organic compound used for thecomposite material is preferably an organic compound having a highhole-transport property. Specifically, a substance having a holemobility of 10⁻⁶ cm²/Vs or higher is preferably used. However, anysubstance other than the above substances may also be used as long as itis a substance in which the hole-transport property is higher than theelectron-transport property. The organic compounds which can be used forthe composite material are specifically shown below.

For example, as the organic compounds that can be used for the compositematerial, there are aromatic amine compounds such as MTDATA, TDATA,DPAB, DNTPD, DPA3B, PCzPCA1, PCzPCA2, PCzPCN1,4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB orα-NPD), andN,N′-bis(3-methylphenyl)-N,N′-diphenyl[1,1′-biphenyl]-4,4′-diamine(abbreviation: TPD); and carbazole derivatives such as4,4′-di(N-carbazolyl)biphenyl (abbreviation: CBP),1,3,5-tris[4-(N-carbazolyl)phenyl]benzene (abbreviation: TCPB),9-[4-(N-carbazolyl)]phenyl-10-phenylanthracene (abbreviation: CzPA), and1,4-bis[4-(N-carbazolyl)phenyl-2,3,5,6-tetraphenylbenzene. Note that thefluorene derivative of an embodiment of the present invention which isdescribed in Embodiment 1 can also be used in a similar manner.

Further, there are aromatic hydrocarbon compounds such as2-tert-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t-BuDNA),2-tert-butyl-9,10-di(1-naphthyl)anthracene,9,10-bis(3,5-diphenylphenyl)anthracene (abbreviation: DPPA),2-tert-butyl-9,10-bis(4-phenylphenyl)anthracene (abbreviation: t-BuDBA),9,10-di(2-naphthyl)anthracene (abbreviation: DNA),9,10-diphenylanthracene (abbreviation: DPAnth), 2-tert-butylanthracene(abbreviation: t-BuAnth), 9,10-bis(4-methyl-1-naphthyl)anthracene(abbreviation: DMNA),9,10-bis[2-(1-naphthyl)phenyl)-2-tert-butylanthracene,9,10-bis[2-(1-naphthyl)phenyl]anthracene, and2,3,6,7-tetramethyl-9,10-di(1-naphthyl)anthracene.

Furthermore, there are aromatic hydrocarbon compounds such as2,3,6,7-tetramethyl-9,10-di(2-naphthyl)anthracene, 9,9′-bianthryl,10,10′-diphenyl-9,9′-bianthryl,10,10′-bis(2-phenylphenyl)-9,9′-bianthryl,10,10′-bis[(2,3,4,5,6-pentaphenyl)phenyl]-9,9′-bianthryl, anthracene,tetracene, rubrene, perylene, 2,5,8,11-tetra(tert-butyl)perylene,pentacene, coronene, 4,4′-bis(2,2-diphenylvinyl)biphenyl (abbreviation:DPVBi), and 9,10-bis[4-(2,2-diphenylvinyl)phenyl]anthracene(abbreviation: DPVPA).

As a substance having an acceptor property, organic compounds such as7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (abbreviation:F₄-TCNQ) and chloranil, and a transition metal oxide can be given. Inaddition, oxides of metals belonging to Groups 4 to 8 in the periodictable can be also given. Specifically, vanadium oxide, niobium oxide,tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide,manganese oxide, and rhenium oxide are preferable since theirelectron-accepting property is high. Among these, molybdenum oxide isespecially preferable since it is stable in the air and its hygroscopicproperty is low and is easily treated.

Note that for the first layer 111, a composite material formed using anyof the above-mentioned high molecular compounds such as PVK, PVTPA,PTPDMA, or Poly-TPD and any of the above-mentioned acceptor substancesmay be used. Note that a composite material, which is formed combiningthe fluorene derivative of an embodiment of the present invention whichis described in Embodiment 1 with the above substance having an acceptorproperty, can also be used for the first layer 111.

The second layer 112 which is a hole-transport layer includes asubstance having a high hole-transport property. Note that the fluorenederivative of an embodiment of the present invention which is describedin Embodiment 1 is used for the second layer 112 in Embodiment 2. Sincethe above fluorene derivative of an embodiment of the present inventionhas a wide band gap, the second layer 112 formed using the fluorenederivative hardly absorbs exciton energy generated in the third layer(light-emitting layer) 113 which is an adjacent to the second layer 112and excitons can be efficiently confined in the light-emitting layer.Thus, a light-emitting element with high efficiency can be obtained.

Further, the fluorene derivative of an embodiment of the presentinvention which is described in Embodiment 1 can be used for both thefirst layer 111 and the second layer 112. In this case, an element canbe easily formed and the use efficiency of the material can be improved.Moreover, since energy diagrams of the first layer 111 and the secondlayer 112 are the same or similar, carriers can be transported easilybetween the first layer 111 and the second layer 112.

The third layer 113 is a layer including a substance having a highlight-emitting property. Low molecular organic compounds described belowcan be used for the third layer 113. Note that since the fluorenederivative of an embodiment of the present invention which is describedin Embodiment 1 has a light-emitting property, the fluorene derivativecan also be used as a light-emitting material.

As a light-emitting substance, for example, a fluorescent compound whichemits fluorescence or a phosphorescent compound which emitsphosphorescence can be used.

As a fluorescent compound which can be used for the light-emitting layer113, for example, as a light-emitting substance for blue emission, thereareN,N′-bis[4-(9H-carbazol-9-yl)phenyl]-N,N′-diphenylstilbene-4,4′-diamine(abbreviation: YGA2S),4-(9H-carbazol-9-yl)-4′-(10-phenyl-9-anthryl)triphenylamine(abbreviation: YGAPA), and the like.

As a light-emitting substance for green emission, there areN-(9,10-diphenyl-2-anthryl)-N,9-diphenyl-9H-carbazol-3-amine(abbreviation: 2PCAPA),N-[9,10-bis(1,1′-biphenyl-2-yl)-2-anthryl]-N,9-diphenyl-9H-carbazol-3-amine(abbreviation: 2PCABPhA),N-(9,10-diphenyl-2-anthryl)-N,N′,N′-triphenyl-1,4-phenylenediamine(abbreviation: 2DPAPA),N-[9,10-bis(1,1′-biphenyl-2-yl)-2-anthryl]-N,N′,N′-triphenyl-1,4-phenylenediamine(abbreviation: 2DPABPhA),9,10-bis(1,1′-biphenyl-2-yl)-N-[4-(9H-carbazol-9-yl)phenyl]-N-phenylanthracen-2-amine(abbreviation: 2YGABPhA), N,N,9-triphenylanthracen-9-amine(abbreviation: DPhAPhA), and the like.

As a light-emitting substance for yellow emission, there are rubrene,5,12-bis(1,1′-biphenyl-4-yl)-6,11-diphenyltetracene (abbreviation: BPT),and the like. Furthermore, as a light-emitting substance for redemission, there areN,N,N′,N′-tetrakis(4-methylphenyl)tetracene-5,11-diamine (abbreviation:p-mPhTD),7,14-diphenyl-N,N′,N′-terakis(4-methylphenyl)acenaphtho[1,2-a]fluoranthene-3,10-diamine(abbreviation: p-mPhAFD), and the like.

As a phosphorescent compound which can be used as the light-emittinglayer 113, for example, as a substance for blue light emission,bis[2-(4′,6′-difluorophenyl)pyridinato-N,C^(2′)]iridium(III)tetrakis(1-pyrazolyl)borate(abbreviation: FIr6),bis[2-(4′,6′-difluorophenyl)pyridinato-N,C^(2′)]iridium(II)picolinate(abbreviation: FIrpic),bis{2-[3′,5′-bis(trifluoromethyl)phenyl]pyridinato-N,C^(2′)}iridium(III)picolinate (abbreviation: Ir(CF₃ppy)₂(pic));bis[2-(4′,6′-difluorophenyl)pyridinato-N,C^(2′)]iridium(III)acetylacetonate(abbreviation: FIr(acac)), or the like can be given. As a substance forgreen light emission, tris(2-phenylpyridinato-N,C^(2′))iridium(III)(abbreviation: Ir(ppy)₃),bis[2-phenylpyridinato-N,C^(2′)]iridium(III)acetylacetonate(abbreviation: Ir(ppy)₂(acac)),bis(1,2-diphenyl-1H-benzimidazolato)iridium(III)acetylacetonate(abbreviation: Ir(pbi)₂(acac)),bis(benzo[h]quinolinato)iridium(III)acetylacetonate (abbreviation:Ir(bzq)₂(acac)), or the like can be given. As a substance for yellowlight emission,bis(2,4-diphenyl-1,3-oxazolato-N,C^(2′))iridium(III)acetylacetonate(abbreviation: Ir(dpo)₂(acac)),bis[2-(4′-perfluorophenylphenyl)pyridinato]iridium(III)acetylacetonate(abbreviation: Ir(p-PF-ph)₂(acac)),bis(2-phenylbenzothiazolato-N,C^(2′))iridium(III)acetylacetonate(abbreviation: Ir(bt)₂(acac)), or the like can be given. As a substancefor orange light emission,tris(2-phenylquinolinato-N,C^(2′))iridium(III) (abbreviation: Ir(pq)₃),bis(2-phenylquinolinato-N,C^(2′))iridium(III)acetylacetonate(abbreviation: Ir(pq)₂(acac)), or the like can be given. As a substancefor red light emission, an organometallic complex such asbis[2-(2′-benzo[4,5-a]thienyl)pyridinato-N,C^(3′)]iridium(III)acetylacetonate(abbreviation: Ir(btp)₂(acac)),bis(1-phenylisoquinolinato-N,C^(2′))iridium(III)acetylacetonate(abbreviation: Ir(piq)₂(acac)),(acetylacetonato)bis[2,3-bis(4-fluorophenyl)quinoxalinato]iridium(III)(abbreviation: Ir(Fdpq)₂(acac)),2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrinatoplatinum(II)(abbreviation: PtOEP), or the like can be given. In addition, a rareearth metal complex such astris(acetylacetonato)(monophenanthroline)terbium(III) (abbreviation:Tb(acac)₃(Phen)),tris(1,3-diphenyl-1,3-propanedionato)(monophenanthroline)europium(III)(abbreviation: Eu(DBM)₃(Phen)), ortris[1-(2-thenoyl)-3,3,3-trifluoroacetonato](monophenanthroline)europium(III)(abbreviation: Eu(TTA)₃(Phen)) exhibits light emission from a rare earthmetal ion (electron transition between different multiplicities);therefore, such a rare earth metal complex can be used as aphosphorescent compound.

The third layer 113 may have a structure in which the above-describedsubstance having a high light-emitting property is dispersed in anothersubstance. Note that in the case of the dispersing, the concentration ofthe substance to be dispersed (a dopant) is preferably 20% or less ofthe total in mass ratio. Further, as a substance in which the substancehaving a light-emitting property is dispersed (a host), a knownsubstance can be used. It is preferable to use a substance having alowest unoccupied molecular orbital level (LUMO level) shallower (theabsolute value is smaller) than that of the substance having alight-emitting property and having a highest occupied molecular orbitallevel (HOMO level) deeper (the absolute value is larger) than that ofthe substance having a light-emitting property (the dopant). Further, itis preferable that the band gap (Bg: a difference between a HOMO leveland a LUMO level) of the host be larger than the Bg of the dopant havinga light-emitting property. Furthermore, when the light emitted from thedopant is fluorescent, in the S1 level, the dopant is preferably higherthan the host, and when the light emitted from the dopant isphosphorescent, in the T1 level, the dopant is preferably higher thanthe host.

Specifically, a metal complex such as tris(8-quinolinolato)aluminum(III)(abbreviation: Alq), tris(4-methyl-8-quinolinolato)aluminum(II)(abbreviation: Almq₃), bis(10-hydroxybenzo[h]quinolinato)beryllium(II)(abbreviation: BeBq₂),bis(2-methyl-8-quinolinolato)(4-phenylpbenolato)aluminum(III)(abbreviation: BAlq), bis(8-quinolinolato)zinc(II) (abbreviation: Znq),bis[2-(2-benzoxazolyl)phenolato]zinc(II) (abbreviation: ZnPBO), orbis[2-(2-benzothiazolyl)phenolato]zinc(II) (abbreviation: ZnBTZ) can beused.

In addition, a heterocyclic compound such as2-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (abbreviation:PBD), 1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]benzene(abbreviation: OXD-7),3-(biphenyl-4-yl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole(abbreviation: TAZ),2,2′,2″-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole)(abbreviation: TPBI), bathophenanthroline (abbreviation: BPhen), orbathocuproine (BCP) can be used.

Alternatively, a condensed aromatic compound such as9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPA),3,6-diphenyl-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: DPCzPA), 9,10-bis(3,5-diphenylphenyl)anthracene(abbreviation: DPPA), 9,10-di(2-naphthyl)anthracene (abbreviation: DNA),2-tert-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t-BuDNA),9,9′-bianthryl (abbreviation: BANT),9,9′-(stilbene-3,3′-diyl)diphenanthrene (abbreviation: DPNS),9,9′-(stilbene-4,4′-diyl)diphenanthrene (abbreviation: DPNS2), or3,3′,3″-(benzene-1,3,5-triyl)tripyrene (abbreviation: TPB3) can also beused.

As a substance in which the substance having a light-emitting propertyis dispersed, a plurality of kinds of substances can be used. Forexample, in order to suppress crystallization, a substance such asrubrene which suppresses crystallization, may be further added. Inaddition, NPB, Alq, or the like can be further added in order toefficiently transfer energy to the substance having a light-emittingproperty. Note that the fluorene derivative of an embodiment of thepresent invention which is described in Embodiment 1 can be used. With astructure in which a substance having a high light-emitting property isthus dispersed in another substance, crystallization of the third layer113 can be suppressed. Further, concentration quenching which resultsfrom the high concentration of the substance having a highlight-emitting property can also be suppressed.

Further, in particular, among the above-described substances, asubstance having an electron-transport property is preferably used sothat a substance having a light-emitting property is dispersed thereinto form the third layer 113. Specifically, it is also possible to useany of the above metal complexes and heterocyclic compounds; CzPA, DNA,and t-BuDNA among the above condensed aromatic compounds; and furthermacromolecular compounds which will be given later as a substance thatcan be used for the fourth layer 114.

Alternatively, for the third layer 113, high molecular compounds givenbelow can also be used.

As a light-emitting substance for blue emission, there arepoly(9,9-dioctylfluorene-2,7-diyl) (abbreviation: PFO),poly[(9,9-dioctylfluorene-2,7-diyl-co-(2,5-dimethoxybenzene-1,4-diyl)](abbreviation: PF-DMOP),poly{(9,9-dioctylfluorene-2,7-diyl)-co-[N,N′-di-(p-butylphenyl)-1,4-diaminobenzene]}(abbreviation: TAB-PFH), and the like.

As a light-emitting substance for green emission, there arepoly(p-phenylenevinylene) (abbreviation: PPV),poly[(9,9-dihexylfluorene-2,7-diyl)-alt-co-(benzo[2,1,3]thiadiazol-4,7-diyl)](abbreviation: PFBT),poly[(9,9-dioctyl-2,7-divinylenefluorenylene)-alt-co-(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene)],and the like.

As a light-emitting substance for orange to red emission, there arepoly[2-methoxy-5-(2′-ethylhexoxy)-1,4-phenylenevinylene] (abbreviation:MEH-PPV), poly(3-butylthiophene-2,5-diyl) (abbreviation: R⁴-PAT),poly{[9,9-dihexyl-2,7-bis(1-cyanovinylene)fluorenylene]-alt-co-[2,5-bis(N,N′-diphenylamino)-1,4-phenylene]},poly{[2-methoxy-5-(2-ethylhexyloxy)-1,4-bis(1-cyanovinylenephenylene)]-alt-co-[2,5-bis(N,N′-diphenylamino)-1,4-phenylene]}(abbreviation: CN-PPV-DPD), and the like.

The light-emitting layer 113 may be a stack of two or more layers. Forexample, in the case where the light-emitting layer 113 is formed bystacking a first light-emitting layer and a second light-emitting layerin that order from the hole transport layer side, the firstlight-emitting layer can be formed using a substance having a holetransport property as the host material and the second light-emittinglayer can be formed using a substance having an electron transportproperty as the host material. It is more preferable that a material inwhich the hole-transport property is higher than the electron-transportproperty be used for the host material of the first light-emitting layerand a material in which the electron-transport property is higher thanthe hole-transport property be used for the host material of the secondlight-emitting layer. With the above structure, a light emission site isformed between the first light-emitting layer and the secondlight-emitting layer, whereby an element having higher efficiency can beobtained.

When the light-emitting layer having the structure described above isformed using a plurality of materials, the light-emitting layer can beformed using co-evaporation by a vacuum evaporation method; or anink-jet method, a spin coating method, a dip coating method, or the likeas a method for mixing a solution.

The fourth layer 114 is an electron-transport layer that includes asubstance having a high electron-transport property. For the fourthlayer 114, for example, as a low molecular organic compound, a metalcomplex such as Alq, Almq₃, BeBq₂, BAlq, Znq, ZnPBO, or ZnBTZ can beused. Alternatively, instead of the metal complex, a heterocycliccompound such as PBD, OXD-7, TAZ, TPBI, BPhen, or BCP can be used. Thesubstances mentioned here are mainly ones that have an electron mobilityof 10⁻⁶ cm²/Vs or higher. Note that any substance other than the abovesubstances may be used for the electron-transport layer as long as it isa substance in which the electron-transport property is higher than thehole-transport property. Furthermore, the electron transport layer isnot limited to a single layer, and two or more layers made of theaforementioned substances may be stacked.

For the fourth layer 114, a high molecular compound can also be used.For example, poly[(9,9-dihexylfluorene-2,7-diyl)-co-(pyridine-3,5-diyl)](abbreviation: PF-Py),poly[(9,9-dioctylfluorene-2,7-diyl)-co-(2,2′-bipyridin-6,6′-diyl)](abbreviation: PF-BPy), or the like can be used.

The fifth layer 115 is an electron-inject layer that includes asubstance having a high electron-inject property. For the fifth layer115, an alkali metal, an alkaline earth metal, or a compound thereof,such as lithium fluoride (LiF), cesium fluoride (CsF), or calciumfluoride (CaF₂), can be used. Alternatively, a layer of anelectron-transport substance which contains an alkali metal, an alkalineearth metal, or a compound thereof, specifically, a layer of Alq whichcontains magnesium (Mg), or the like may be used. Note that in thiscase, electrons can be more efficiently injected from the secondelectrode 104.

For the second electrode 104, a metal, an alloy, an electricallyconductive compound, a mixture thereof, or the like which has a low workfunction (specifically, a work function of 3.8 eV or less) can be used.As a specific example of such a cathode material, an element thatbelongs to Group 1 or 2 of the periodic table, that is, alkali metalssuch as lithium (Li) and cesium (Cs), alkaline earth metals such asmagnesium (Mg), calcium (Ca), and strontium (Sr), alloys containingthese (e.g., MgAg and AlLi), rare earth metals such as europium (Eu) andytterbium (Yb), alloys containing these, and the like can be given.

Note that in the case where the second electrode 104 is formed using analkali metal, an alkaline earth metal, or an alloy thereof, a vacuumevaporation method or a sputtering method can be used. In the case ofusing a silver paste or the like, a coating method, an inkjet method, orthe like can be used

Note that by provision of the fifth layer 115, the second electrode 104can be formed using any of a variety of conductive materials such as Al,Ag, ITO, and indium oxide-tin oxide containing silicon or silicon oxideregardless of the work functions. A film of such a conductive materialcan be formed by a sputtering method, an inkjet method, a spin coatingmethod, or the like.

Further, as a formation method of the EL layer 103 in which the firstlayer (bole-injection layer) 111, the second layer (hole-transportlayer) 112, the third layer (light-emitting layer) 113, the fourth layer(electron-transport layer) 114, and the fifth layer (electron-injectionlayer) 115 are in that order stacked, any of a variety of methods can beemployed regardless of whether the method is a dry process or a wetprocess. For example, a vacuum evaporation method, an inkjet method, aspin coating method, or the like can be used. Note that a differentformation method may be employed for each layer.

The second electrode 104 can also be formed by a wet process such as asol-gel method using a paste of a metal material instead of a dryprocess such as a sputtering method or a vacuum evaporation method.

Since holes mainly flow between the first electrode 102 and the firstlayer (hole-injection layer) 111, between the first layer(hole-injection layer) 111 and the second layer (hole-transport layer)112, and between the second layer (hole-transport layer) 112 and thethird layer (light-emitting layer) 113, the HOMO levels (work functionin a case of metal) thereof are preferably the same or almost the sameto reduce the carrier injection barrier between the adjacent layers.Similarly, electrons mainly flow between the third layer (light-emittinglayer) 113 and the fourth layer (electron-transport layer) 114, betweenthe fourth layer (electron-transport layer) 114 and the fifth layer(electron-injection layer) 115, and between the fifth layer(electron-injection layer) 115 and the second electrode 104, the LUMOlevels (work function in a case of metal) thereof are preferably thesame or almost the same to reduce the carrier injection barrier betweenthe adjacent layers. The difference is preferably less than or equal to0.2 eV, more preferably less than or equal to 0.1 eV.

It is preferable that a difference in the HOMO level between the secondlayer (hole-transport layer) 112 and the third layer (light-emittinglayer) 113 and a difference in the LUMO level between the third layer(light-emitting layer) 113 and the fourth layer (electron-transportlayer) 114 be increased to confine carriers in the light-emitting layer,so that a light-emitting element with higher efficiency can be obtained.Note that in this case, when a barrier is too high, a driving voltage ishigh, which becomes a burden on the element. Therefore, each thedifference is preferably less than or equal to 0.4 eV, more preferablyless than or equal to 0.2 eV.

In the above-described light-emitting element of an embodiment of thepresent invention, a current flows because of a potential differencegenerated between the first electrode 102 and the second electrode 104and holes and electrons recombine in the EL layer 103, so that light isemitted. Then, this emitted light is extracted out through one or bothof the first electrode 102 and the second electrode 104. Accordingly,one of or both the first electrode 102 and the second electrode 104is/are an electrode having a light-transmitting property.

As illustrated in FIG. 2A, when only the first electrode 102 has alight-transmitting property, the emitted light is extracted from asubstrate side through the first electrode 102. Alternatively, asillustrated in FIG. 2B, when only the second electrode 104 has alight-transmitting property, the emitted light is extracted from theside opposite to the substrate 101 through the second electrode 104. Asillustrated in FIG. 2C, when each of the first electrode 102 and thesecond electrode 104 has a light-transmitting property, the emittedlight is extracted from both the substrate 101 side and the sideopposite to the substrate 101 side through the first electrode 102 andthe second electrode 104.

The structure of the layers provided between the first electrode 102 andthe second electrode 104 is not limited to the aforementioned one.Structures other than the above may be employed as long as at least thesecond layer 112 which is a hole-transport layer and the third layer 113which is a light-emitting layer are included.

Alternatively, as illustrated in FIG. 1B, a structure may be employed inwhich the second electrode 104 functioning as a cathode, the EL layer103, and the first electrode 102 functioning as an anode are stacked inthat order over the substrate 101. Note that the EL layer 103 in thiscase has a structure in which the fifth layer 115, the fourth layer 114,the third layer 113, the second layer 112, the first layer 111, and thefirst electrode 102 are stacked in that order over the second electrode104.

Note that by use of the light-emitting element of the present invention,a passive matrix light-emitting device or an active matrixlight-emitting device in which drive of the light-emitting element iscontrolled by a thin film transistor (TFT) can be fabricated.

Note that there is no particular limitation on the structure of the TFTin the case of fabricating an active matrix light-emitting device. Forexample, a staggered TFT or an inverted staggered TFT can be used asappropriate. Further, a driver circuit formed over a TFT substrate maybe formed using both of an n-type TFT and a p-type TFT or only either ann-type TFT or a p-type TFT. Furthermore, there is no particularlimitation on the crystallinity of a semiconductor film used for theTFT. An amorphous semiconductor film may be used, or a crystallinesemiconductor film may be used.

Since the second layer (hole-transport layer) 112 is formed using thefluorene derivative of an embodiment of the present invention, in thelight-emitting element which is described in Embodiment 2, not onlyimprovement in element efficiency but also suppression of powerconsumption can be realized.

(Embodiment 3)

In Embodiment 3, a mode of a light-emitting element having a structurein which a plurality of light-emitting units (also referred to as ELlayers) is stacked (hereinafter, referred to as a stacked-type element)is described with reference to FIGS. 3A and 3B. The light-emittingelement is a stacked-type light-emitting element including a pluralityof light-emitting units between a first electrode and a secondelectrode. Each structure of the light-emitting units can be similar tothat described in Embodiment 2. In other words, the light-emittingelement described in Embodiment 2 is a light-emitting element having onelight-emitting unit. In Embodiment 3, a light-emitting element having aplurality of light-emitting units is described.

In FIG. 3A, a first light-emitting unit 511 and a second light-emittingunit 512 are stacked between a first electrode 521 and a secondelectrode 522. The first electrode 521 and the second electrode 522 canbe similar to those in Embodiment 2. The first light-emitting unit 511and the second light-emitting unit 512 may have the same structure ordifferent structures, and a structure similar to those described inEmbodiment 2 can be employed.

A charge-generation layer 513 is a layer which injects electrons intothe light-emitting unit on one side and injects holes into thelight-emitting unit on the other side when voltage is applied to thefirst electrode 521 and the second electrode 522, and may have either asingle layer structure or a stacked structure of plural layers. As astacked structure of plural layers, a structure in which a layer thatinjects holes and a layer that injects electrons are stacked ispreferable.

As the layer that injects holes, a semiconductor or an insulator, suchas molybdenum oxide, vanadium oxide, rhenium oxide, or ruthenium oxide,can be used. Alternatively, the layer that injects holes may have astructure in which an acceptor substance is added to a substance havinga high hole-transport property. The layer including a substance having ahigh hole-transport property and an acceptor substance includes, as anacceptor substance, 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane(abbreviation: F₄-TCNQ) or metal oxide such as vanadium oxide,molybdenum oxide, or tungsten oxide. As the substance having a highhole-transport property, a variety of compounds such as an aromaticamine compound, a carbazole derivative, aromatic hydrocarbon, ahigh-molecular compound, oligomer, dendrimer, polymer, and the like canbe used. Note that the fluorene derivative of an embodiment of thepresent invention which is described in Embodiment 1 can also be used ina similar manner. Note that a substance having a hole mobility of 10⁻⁶cm²/Vs or higher is preferably employed as the substance having a highhole-transport property. However, any substance other than the abovesubstances may also be used as long as it is a substance in which thehole-transport property is higher than the electron-transport property.Since the composite material of the substance having a highhole-transport property and the acceptor substance has an excellentcarrier-injection property and an excellent carrier-transport property,low-voltage driving and low-current driving can be realized.

As the layer that injects electrons, a semiconductor or an insulator,such as lithium oxide, lithium fluoride, or cesium carbonate, can beused. Alternatively, the hole-injection layer may have a structure inwhich a donor substance is added to a substance having a highhole-transport property. As the donor substance, an alkali metal, analkaline earth metal, a rare-earth metal, a metal that belongs to Group13 of the periodic table, or an oxide or carbonate thereof can be used.Specifically, lithium (Li), cesium (Cs), magnesium (Mg), calcium (Ca),ytterbium (Yb), indium (In), lithium oxide, cesium carbonate, or thelike is preferably used. Alternatively, an organic compound such astetrathianaphthacene may be used as the donor substance. As thesubstance having a high electron-transport property, the materialsdescribed in Embodiment 1 can be used. Note that a substance having ahole mobility of 10⁻⁶ cm²/Vs or higher is preferably employed as thesubstance having a high hole-transport property. However, any substanceother than the above substances may also be used as long as it is asubstance in which the electron-transport property is higher than thehole-transport property. Since the composite material of the substancehaving a high hole-transport property and the donor substance has anexcellent carrier-injection property and an excellent carrier-transportproperty, low-voltage driving and low-current driving can be realized.

Further, the electrode materials described in Embodiment 2 can be usedfor the charge-generation layer 513. For example, the charge-generationlayer 513 may be formed with a combination of a layer including asubstance having a high hole-transport property and metal oxide and atransparent conductive film. It is preferable that the charge-generationlayer 513 be a highly light-transmitting layer in terms of lightextraction efficiency.

In any case, the charge-generation layer 513, which is interposedbetween the first light-emitting unit 511 and the second light-emittingunit 512, is acceptable as long as a layer which injects electrons intothe light-emitting unit on one side and injects holes into thelight-emitting unit on the other side when voltage is applied to thefirst electrode 521 and the second electrode 522. For example, anystructure is acceptable for the charge-generation layer 513 as long asthe charge-generation layer 513 injects electrons and holes into thefirst light-emitting unit 511 and the second light-emitting unit 512,respectively, when voltage is applied so that the potential of the firstelectrode is higher than the potential of the second electrode.

In Embodiment 3, the light-emitting element having two light-emittingunits is described; however, an embodiment of the present invention canbe similarly applied to a light-emitting element in which three or morelight-emitting units are stacked as illustrated in FIG. 3B. Byarrangement of a plurality of light-emitting units, which arepartitioned by the charge-generation layer 513 between a pair ofelectrodes, as in the light-emitting element of Embodiment 3, lightemission in a high luminance region can be achieved with current densitykept low, thus light-emitting having long lifetime can be realized. Whenthe light-emitting element is applied for a lighting device as anapplication example, voltage drop due to resistance of an electrodematerial can be reduced, thereby achieving homogeneous light emission ina large area. Moreover, a light-emitting device with low powerconsumption, which can be driven at low voltage, can be achieved.

The light-emitting units emit light having different colors from eachother, thereby obtaining light emission of a desired color as the wholelight-emitting element. For example, in a light-emitting element havingtwo light-emitting units, the emission colors of the firstlight-emitting unit and the second light-emitting unit are madecomplementary, so that the light-emitting element which emits whitelight as the whole light-emitting element can be obtained. Note that theword “complementary” means color relationship in which an achromaticcolor is obtained when colors are mixed. That is, white light emissioncan be obtained by mixture of light obtained from substances emittingthe lights of complementary colors. The same can be applied to alight-emitting element which has three light-emitting units. Forexample, the light-emitting element as a whole can provide white lightemission when the emission color of the first light-emitting unit isred, the emission color of the second light-emitting unit is green, andthe emission color of the third light-emitting unit is blue.

Note that Embodiment 3 can be combined with any other embodiment asappropriate.

(Embodiment 4)

In Embodiment 4, a light-emitting device having a light-emitting elementof the present invention in a pixel portion is described with referenceto FIGS. 4A and 4B. FIG. 4A is a top view illustrating a light-emittingdevice while FIG. 4B is a cross-sectional view taken along lines A-A′and B-B′ of FIG. 4A.

In FIG. 4A, reference numeral 401 denotes a driver circuit portion (asource side driver circuit), reference numeral 402 denotes a pixelportion, and reference numeral 403 denotes a driver circuit portion (agate side driver circuit), which are shown by a dotted line. Referencenumeral 404 denotes a sealing substrate, reference numeral 405 denotes asealant, and a portion enclosed by the sealant 405 is a space 407.

Note that a lead wiring 408 is a wiring for transmitting signals thatare to be inputted to the source side driver circuit 401 and the gateside driver circuit 403, and receives a video signal, a clock signal, astart signal, a reset signal, and the like from a flexible printedcircuit (FPC) 409 which serves as an external input terminal Althoughonly the FPC is illustrated here, a printed wiring board (PWB) may beattached to the FPC. The light-emitting device in this specificationincludes not only a light-emitting device itself but also alight-emitting device to which an FPC or a PWB is attached.

Next, a cross-sectional structure is described with reference to FIG.4B. The driver circuit portion and the pixel portion are formed over anelement substrate 410. In this case, one pixel in the pixel portion 402and the source side driver circuit 401 which is the driver circuitportion are illustrated. A CMOS circuit, which is a combination of ann-channel TFT 423 with a p-channel TFT 424, is formed as the source sidedriver circuit 401. Such a driver circuit may be formed using a varietyof circuits such as a CMOS circuit, a PMOS circuit, or an NMOS circuitAlthough a driver-integrated type in which a driver circuit is formedover the substrate is described in Embodiment 4, the present inventionis not limited to this type, and the driver circuit can be formedoutside the substrate.

The pixel portion 402 includes a plurality of pixels having a switchingTFT 411, a current control TFT 412, and a first electrode 413electrically connected to a drain of the current control TFT 412. Notethat an insulator 414 is formed to cover an end portion of the firstelectrode 413.

In order to improve the coverage, the insulator 414 is preferablyprovided such that either an upper end portion or a lower end portion ofthe insulator 414 has a curved surface with a curvature. For example,when positive photosensitive acrylic is used as a material for theinsulator 414, only an upper end portion of the insulator 414 can have acurved surface with a radius of curvature (0.2 μm to 3 μm).Alternatively, the insulator 414 can be formed using either a negativetype photosensitive material that becomes insoluble in an etchant bylight irradiation or a positive type photosensitive material thatbecomes soluble in an etchant by light irradiation.

Over the first electrode 413, an EL layer 416 and a second electrode 417are formed. In this case, the first electrode 413 can be formed usingany of a variety of materials such as metals, alloys, and electricallyconductive compounds or a mixture thereof. Note that as specificmaterials, the materials described in Embodiment 2 as a material thatcan be used for the first electrode can be used.

The EL layer 416 is formed by any of a variety of methods such as anevaporation method using an evaporation mask, an inkjet method, and aspin coating method. The EL layer 416 has any of the structuresdescribed in Embodiment 2. Further, as another material included in theEL layer 416, low molecular compounds or high molecular compounds(including oligomers and dendrimers) may be used. As the material forthe EL layer, not only an organic compound but also an inorganiccompound may be used.

The second electrode 417 can be formed using any of a variety of metals,alloys, and electrically conductive compounds, or a mixture thereof.Among such materials, a metal, an alloy, an electrically conductivecompound, a mixture thereof, or the like having a low work function (awork function of 3.8 eV or less) is preferably used when the secondelectrode 417 is used as a cathode. As an example, an element belongingto Group 1 or Group 2 in the periodic table, i.e., an alkali metal suchas lithium (Li) or cesium (Cs), an alkaline earth metal such asmagnesium (Mg), calcium (Ca), or strontium (Sr), an alloy containing anyof these (e.g., MgAg and AlLi) and the like can be given.

Note that when light generated in the EL layer 416 is transmittedthrough the second electrode 417, the second electrode 417 can be formedusing a stack of a thin metal film with a small thickness and atransparent conductive film (indium oxide-tin oxide (ITO), indiumoxide-tin oxide containing silicon or silicon oxide, indium oxide-zincoxide (IZO), indium oxide containing tungsten oxide and zinc oxide, orthe like).

The sealing substrate 404 is attached to the element substrate 410 withthe sealant 405; thus, a light-emitting element 418 is provided in thespace 407 enclosed by the element substrate 410, the sealing substrate404, and the sealant 405. It is to be noted that the space 407 is filledwith a filler such as an inert gas (e.g., nitrogen or argon) or thesealant 405.

Note that as the sealant 405, an epoxy-based resin is preferably used. Amaterial used for these is desirably a material which does not transmitmoisture or oxygen as possible. As a material for the sealing substrate404, a glass substrate, a quartz substrate, or a plastic substrateincluding fiberglass-reinforced plastics (FRP), polyvinyl fluoride(PVF), polyester, acrylic, or the like can be used.

As described above, the active matrix light-emitting device having thelight-emitting element of the present invention can be obtained.

Further, the light-emitting element of the present invention can be usedfor a passive matrix light-emitting device instead of the above activematrix light-emitting device. FIGS. 5A and 5B illustrate a perspectiveview and a cross-sectional view of a passive matrix light-emittingdevice using the light-emitting element of the present invention. FIG.5A is a perspective view of the light-emitting device, and FIG. 5B is across-sectional view taken along line X-Y of FIG. 5A.

In FIGS. 5A and 5B, an EL layer 504 is provided between a firstelectrode 502 and a second electrode 503 over a substrate 501. An endportion of the first electrode 502 is covered with an insulating layer505. In addition, a partition layer 506 is provided over the insulatinglayer 505. The sidewalls of the partition layer 506 are aslope so that adistance between both sidewalls is gradually narrowed toward the surfaceof the substrate. In other words, a cross section taken along thedirection of the short side of the partition layer 506 is trapezoidal,and the lower side (a side in contact with the insulating layer 505which is one of a pair of parallel sides of the trapezoidal crosssection) is shorter than the upper side (a side not in contact with theinsulating layer 505 which is the other of the pair of parallel sides).By provision of the partition layer 506 in such a manner, a defect ofthe light-emitting element due to static electricity or the like can beprevented.

Accordingly, the passive matrix light-emitting device having thelight-emitting element of the present invention can be obtained.

Note that any of the light-emitting devices described in Embodiment 4(the active matrix light-emitting device and the passive matrixlight-emitting device) are formed using the light-emitting element ofthe present invention, which has high luminous efficiency, andaccordingly a light-emitting device with low power consumption can beobtained.

Note that in Embodiment 4, an appropriate combination of the structuresdescribed in Embodiments 1 to 3 can be used.

(Embodiment 5)

In Embodiment 5, electronic devices including the light-emitting deviceof the present invention which is described in Embodiment 4 aredescribed. Examples of the electronic devices include cameras such asvideo cameras and digital cameras, goggle type displays, navigationsystems, audio reproducing devices (e.g., car audio systems and audiosystems), computers, game machines, portable information terminals(e.g., mobile computers, cellular phones, portable game machines, andelectronic book readers), image reproducing devices in which a recordingmedium is provided (specifically, devices that are capable ofreproducing recording media such as digital versatile discs (DVDs) andprovided with a display device that can display an image), and the like.Specific examples of these electronic devices are shown in FIGS. 6A to6D.

FIG. 6A illustrates a television set according to an embodiment of thepresent invention, which includes a housing 611, a supporting base 612,a display portion 613, speaker portions 614, video input terminals 615,and the like. In this television set, the light-emitting device of thepresent invention can be applied to the display portion 613. Since thelight-emitting device of the present invention has a feature of highluminous efficiency, a television set with low power consumption can beobtained by application of the light-emitting device of the presentinvention.

FIG. 6B illustrates a computer according to an embodiment of the presentinvention, which includes a main body 621, a housing 622, a displayportion 623, a keyboard 624, an external connection port 625, a pointingdevice 626, and the like. In this computer, the light-emitting device ofthe present invention can be applied to the display portion 623. Sincethe light-emitting device of the present invention has a feature of highluminous efficiency, a computer with low power consumption can beobtained by application of the light-emitting device of the presentinvention.

FIG. 6C shows a cellular phone according to an embodiment of the presentinvention, which includes a main body 631, a housing 632, a displayportion 633, an audio input portion 634, an audio output portion 635,operation keys 636, an external connection port 637, an antenna 638, andthe like. In this cellular phone, the light-emitting device of thepresent invention can be applied to the display portion 633. Since thelight-emitting device of the present invention has a feature of highluminous efficiency, a cellular phone having reduced power consumptioncan be obtained by application of the light-emitting device of thepresent invention.

FIG. 6D shows a camera according to an embodiment of the presentinvention, which includes a main body 641, a display portion 642, ahousing 643, an external connection port 644, a remote control receivingportion 645, an image receiving portion 646, a battery 647, an audioinput portion 648, operation keys 649, an eyepiece portion 650, and thelike. In this camera, the light-emitting device of the present inventioncan be applied to the display portion 642. Since the light-emittingdevice of the present invention has a feature of high luminousefficiency, a camera having reduced power consumption can be obtained byapplication of the light-emitting device of the present invention.

As thus described, application range of the light-emitting device of thepresent invention is quite wide, and this light-emitting device can beapplied to electronic devices of a variety of fields. With use of thelight-emitting device of the present invention, an electronic devicehaving reduced power consumption can be obtained.

Moreover, the light-emitting device of the present invention can be usedas a lighting device. FIG. 7 shows an example of a liquid crystaldisplay device in which the light-emitting device of the presentinvention is used as a backlight. The liquid crystal display deviceillustrated in FIG. 7 includes a housing 701, a liquid crystal layer702, a backlight 703, and a housing 704. The liquid crystal layer 702 isconnected to a driver IC 705. The light-emitting device of the presentinvention is used for the backlight 703, and current is supplied througha terminal 706.

By using the light-emitting device of the present invention as abacklight of a liquid crystal display device as described above, abacklight with low power consumption can be obtained. Further, since thelight-emitting device of the present invention is a surface emittinglighting device and can be formed to have a large area, a larger-areabacklight can also be obtained. Accordingly, a larger-area liquidcrystal display device with low power consumption can be obtained.

FIG. 8 illustrates an example in which the light-emitting device of thepresent invention is used as a desk lamp, which is a lighting device.The desk lamp illustrated in FIG. 8 has a housing 801 and a light source802, and the light-emitting device of the present invention is used asthe light source 802. The light-emitting device of the present inventionhas the light-emitting element having high luminous efficiency andtherefore can be used as a desk lamp with low power consumption.

FIG. 9 illustrates an example in which a light-emitting device to whichthe present invention is applied is used as an interior lighting device901. Since the light-emitting device of the present invention can beenlarged, the light-emitting device can be used as a large-area lightingdevice. Further, the light-emitting device of the present invention hasthe light-emitting element having high luminous efficiency and thereforecan be used as a lighting device with low power consumption. In a roomwhere a light-emitting device to which the present invention is appliedis thus used as the interior lighting device 901, a television set 902according to the present invention as described with reference to FIG.6A may be placed, so that public broadcasting or movies can be watchedthere.

Note that in Embodiment 5, an appropriate combination of the structuresdescribed in Embodiments 1 to 4 can be used.

Example 1 Synthesis Example 1

In Example 1, a synthesis example of the fluorene derivative which isrepresented as General Formula (G1) in Embodiment 1 and an embodiment ofthe present invention is described. Specifically, a synthesis method of4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP),which is represented by Structural Formula (101) in Embodiment 1, isdescribed. A structure of BPAFLP is shown below.

Step 1: Synthesis Method of 9-(4-bromophenyl)-9-phenylfluorene

In a 100-mL three-neck flask, 1.2 g (50 mmol) of magnesium was heatedand stirred under reduced pressure for 30 minutes to be activated. Afterthe flask was cooled to room temperature and was made to have a nitrogenatmosphere, several drops of dibromoethane were added, so that foamformation and heat generation were confirmed. After 12 g (50 mmol) of2-bromobiphenyl dissolved in 10 mL of diethyl ether was slowly droppedinto this mixture, the mixture was stirred and heated under reflux for2.5 hours and made into a Grignard reagent.

In a 500-mL three-neck flask, 10 g (40 mmol) of 4-bromobenzophenone and100 mL of diethyl ether were put. After the Grignard reagent which wassynthesized in advance was slowly dropped into this mixture, the mixturewas heated and stirred under reflux for 9 hours

After the reaction, this mixture was filtrated to obtain a residue. Theobtained residue was dissolved in 150 mL of ethyl acetate, a1N-hydrochloric acid solution was added thereto until the mixed solutionbecame acid, and the mixture was stirred for 2 hours. An organic layerof this solution was washed with water. Then, magnesium sulfate wasadded to remove moisture. This suspension was filtrated and the obtainedfiltrate was concentrated to obtain a candy-like substance.

Then, in a 500-mL recovery flask, this candy-like substance, 50 mL ofglacial acetic acid, and 1.0 mL of hydrochloric acid were put, and themixture was heated and stirred under a nitrogen atmosphere at 130° C.for 1.5 hours to be reacted.

After the reaction, this reaction mixture solution was filtrated toobtain a residue. The obtained residue was washed with water, a sodiumhydroxide aqueous solution, water, and methanol in this order, and thendried, so that 11 g of an objective white powder was obtained at a yieldof 69%. A reaction scheme of the above synthesis method is shown in thefollowing (J-1).

Step 2: Synthesis Method of4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP)

3.2 g (8.0 mmol) of 9-(4-bromophenyl)-9-phenylfluorene, 2.0 g (8.0 mmol)of 4-phenyl-diphenylamine, 1.0 g (10 mmol) of sodium tert-butoxide, and23 mg (0.04 mmol) of bis(dibenzylideneacetone)palladium(0) were added toa 100-mL three-neck flask, and the atmosphere in the flask wassubstituted by nitrogen. Then, 20 mL of dehydrated xylene was added tothis mixture. After the mixture was deaerated while being stirred underreduced pressure, 0.2 mL (0.1 mmol) of tri(tert-butyl)phosphine (10 wt %hexane solution) was added thereto. This mixture was heated and stirredunder a nitrogen atmosphere at 110° C. for 2 hours to be reacted.

After the reaction, 200 ml of toluene was added to the reaction mixturesolution, and the resulting suspension was filtrated through Florisil(produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135)and Celite (Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855).The obtained filtrate was concentrated and purified by silica gel columnchromatography (developing solvent, toluene:hexane=1:4). The obtainedfraction was concentrated, and acetone and methanol were added thereto.The mixture was irradiated with ultrasonic wave and then recrystallizedto obtain 4.1 g of an objective white powder at a yield of 92%. Areaction scheme of the above synthesis method is shown in the following(J-2).

An Rf value of the object by a silica gel thin layer chromatography(TLC) (developing solvent, ethyl acetate:hexane=1:10) was 0.41, that of9-(4-bromophenyl)-9-phenylfluorene was 0.51, and that of4-phenyl-diphenylamine was 0.27.

A compound that was obtained through the above Step 2 was subjected to anuclear magnetic resonance (¹H-NMR) measurement. The measurement dataare shown below. The ¹H-NMR chart is shown in FIGS. 10A and 10B. Themeasurement results show that the fluorene derivative BPAFLP(abbreviation) of the present invention, represented by StructuralFormula (101) was obtained.

¹H-NMR (CDCl₃, 300 MHz): δ (ppm)=6.63-7.02 (m, 3H), 7.06-7.11 (m, 6H),7.19-7.45 (m, 18H), 7.53-7.55 (m, 2H), and 7.75 (d, J=6.9, 2H).

A variety of physical properties of BPAFLP (abbreviation) of theobtained object were measured as described below.

The absorption spectrum (measurement range: 200 nm to 800 nm) wasmeasured using an ultraviolet-visible spectrophotometer (V-550,manufactured by JASCO Corporation). FIG. 11 shows absorption spectra ofa toluene solution and a thin film. The horizontal axis indicates thewavelength (nm) and the vertical axis indicates the absorption intensity(arbitrary unit). The toluene solution put into a quartz cell wasmeasured, and the spectrum in which the absorption spectra of the quartzand toluene were subtracted from the absorption spectrum of the sampleis shown. As the thin film, a sample evaporated on a quartz substratewas measured, and the spectrum in which the absorption spectrum of thequartz was subtracted from the absorption spectrum of the sample isshown. From these spectra, in the case of the toluene solution, anabsorption peak on a long wavelength side was observed at around 314 nm,and in the case of the thin film, an absorption peak on a longwavelength side was observed at around 324 nm.

The emission spectrum was measured using a fluorescencespectrophotometer (FS920, manufactured by Hamamatsu PhotonicsCorporation). FIG. 12 shows emission spectra of a toluene solution and athin film. The horizontal axis indicates 16 the wavelength (nm) and thevertical axis indicates the absorption intensity (arbitrary unit). Thetoluene put into a quartz cell was measured, and as the thin film, asample evaporated on a quartz substrate was measured. From thesespectra, in the case of the toluene solution, the maximum emissionwavelength was observed at 386 nm (excitation wavelength: 330 nm), andin the case of the thin film, the maximum emission wavelength wasobserved at 400 nm (excitation wavelength: 349 nm).

The result of measuring the thin film using a photoelectron spectrometer(AC-2, manufactured by Riken Keiki Co., Ltd.) under the atmosphereindicated that the HOMO level of the thin film was −5.63 eV. The Taucplot of the absorption spectrum of the thin film revealed that theabsorption edge was 3.34 eV. Thus, the energy gap in the solid state wasestimated to be 3.34 eV, which means that the LUMO level of the thinfilm was −2.29 eV. This indicates that BPAFLP (abbreviation) has arelatively deep HOMO level and a wide band gap (Bg).

The characteristics of oxidation-reduction reaction of BPAFLP(abbreviation) were examined by a cyclic voltammetry (CV) measurement.Note that an electrochemical analyzer (ALS model 600A or 600C,manufactured by BAS Inc.) was used for the measurement.

Note that for the measurement of the oxidation characteristic, thepotential of the working electrode with respect to the referenceelectrode was scanned from −0.10 V to 1.50 V and then from 1.50 V to−0.10 V. As a result, the HOMO level was found to be −5.51 [eV]. Inaddition, the oxidation peak took a similar value even after the 100cycles. Accordingly, it was found that repetition of the oxidationreduction between an oxidation state and a neutral state had favorablecharacteristics.

Note that a measurement method is described below.

(Calculation of the Potential Energy of the Reference Electrode withRespect to the Vacuum Level)

First, the potential energy (eV) of the reference electrode (an Ag/Ag⁺electrode) used in Example 1 with respect to the vacuum level wascalculated. In other words, the Fermi level of the Ag/Ag electrode wascalculated. It is known that the oxidation-reduction potential offerrocene in methanol is +0.610 [V vs. SHE] with respect to the normalhydrogen electrode (Reference: Christian R. Goldsmith et al., J. Am.Chem. Soc., Vol. 124, No. 1, 83-96, 2002). On the other hand, using thereference electrode used in Example 1, the oxidation-reduction potentialof ferrocene in methanol was calculated to be +0.11 [V vs. Ag/Ag⁺].Therefore, it was found that the potential energy of the referenceelectrode used in Example 1 was lower than that of the standard hydrogenelectrode by 0.50 [eV].

Note that it is known that the potential energy of the normal hydrogenelectrode from the vacuum level is −4.44 eV (Reference: ToshihiroOhnishi and Tamami Koyama, High molecular EL material, Kyoritsu shuppan,pp. 64-67). Accordingly, the potential energy of the reference electrodeused in Example 1 with respect to the vacuum level could be calculatedto be −4.44-0.50=−4.94 [eV].

(CV Measurement Conditions of the Object)

As for a solution used for the CV measurement, dehydrateddimethylformamide (DMF, product of Sigma-Aldrich Inc., 99.8%, catalogNo. 22705-6) was used as a solvent, and tetra-n-butylammoniumperchlorate (n-Bu₄NClO₄, product of Tokyo Chemical Industry Co., Ltd.,catalog No. T0836), which was a supporting electrolyte, was dissolved inthe solvent such that the concentration of tetra-n-butylammoniumperchlorate was 100 mmol/L. Further, the object to be measured wasdissolved in the solvent such that the concentration thereof was 2mmol/L. A platinum electrode (manufactured by BAS Inc., PTE platinumelectrode) was used as a working electrode, a platinum electrode(manufactured by BAS Inc., Pt counter electrode for VC-3, (5 cm)) wasused as an auxiliary electrode, and an Ag/Ag⁺ electrode (manufactured byBAS Inc., RE-7 reference electrode for nonaqueous solvent) was used as areference electrode. It is to be noted that the measurement wasconducted at room temperature (20° C. to 25° C.). In addition, the scanrate at the CV measurement was set to 0.1 V/sec in all the measurement.

Next, the HOMO level was calculated from the CV measurement. FIG. 13shows the CV measurement results of the oxidation reactioncharacteristics. As shown in FIG. 13, an oxidation peak potential (fromthe neutral state to the oxidation state) E_(pa) was 0.62 V. Inaddition, a reduction peak potential (from the oxidation side to theneutral state) E_(pc) was 0.52 V. Therefore, a half-wave potential (anintermediate potential between E_(pa) and E_(pc), (E_(pa)+E_(pc))/2 [V])can be calculated to be 0.57 V. This shows that oxidization occurs by anelectrical energy of +0.57[V vs. Ag/Ag³⁰ ]. Here, as described above,the potential energy of the reference electrode, which was used inExample 1, with respect to the vacuum level is −4.94 [eV]; therefore, itwas understood that the HOMO level of BPAFLP (abbreviation) wascalculated as follows: −4.94−0.57=−5.51 [eV].

The glass transition temperature was measured with a differentialscanning calorimetry (Pyris 1 DSC, manufactured by Perkin Elmer Co.,Ltd.). According to the measurement results, it was found that the glasstransition temperature was 107° C. In this manner, BPAFLP (abbreviation)had a high glass transition temperature and favorable heat resistance.In addition, the crystallization peak did not exist; thus, it was foundthat BPAFLP (abbreviation) was a substance which is hard to becrystallized.

Example 2 Synthesis Example 2

In Example 2, a synthesis example of the fluorene derivative which isrepresented as General Formula (G1) in Embodiment 1 and an embodiment ofthe present invention is described. Specifically, a synthesis method of4-phenyl-4′-[4-(9-phenylfluoren-9-yl)phenyl]triphenylamine(abbreviation: BPAFLBi), which is represented in Structural Formula(151) in Embodiment 1, is described. A structure of BPAFLBi is shownbelow.

Step 1: Synthesis Method of 9-(4′-bromo-4-biphenyl)-9-phenylfluorene

In a 500-mL three-neck flask, 5.1 g (22 mmol) of 2-bromobiphenyl wasput, and the atmosphere in the flask was substituted by nitrogen. Then,200 mL of dehydrated tetrahydrofuran (abbreviation: THF) was addedthereto and the mixture solution was cooled to −78° C. 14 mL (22 mmol)of an n-butyllithium hexane solution was dropped into this mixturesolution, and the mixture was stirred for 2.5 hours. After that, 6.7 g(20 mmol) of 4-benzoyl-4′-bromobiphenyl was added to this mixture, andthe mixture was stirred at −78° C. for 2 hours and at room temperaturefor 85 hours.

After the reaction, 1N-diluted hydrochloric acid was added to thisreaction solution until the mixed solution became acid, and the mixturewas stirred for 4 hours. This solution was washed with water. After thewashing, magnesium sulfate was added thereto to remove moisture. Thissuspension was filtrated, and the obtained filtrate was concentrated andpurified by silica gel column chromatography (developing solvent,hexane). The obtained fraction was concentrated, methanol was addedthereto, ultrasonic waves were applied thereto, and thenrecrystallization thereof was performed to obtain an objective whitepowder.

Then, in a 200-mL recovery flask, this white powder, 50 mL of glacialacetic acid, and 1.0 mL of hydrochloric acid were put, and the mixturewas heated and stirred under a nitrogen atmosphere at 130° C. for 2.5hours to be reacted.

After the reaction, this reaction mixture solution was filtrated toobtain filtrate. The obtained filtrate was dissolved in 100 mL oftoluene and washed with water, a sodium hydroxide aqueous solution,water in this order, and magnesium sulfate was added thereto to removemoisture. This suspension was filtrated, the obtained filtrate wasconcentrated, and acetone and methanol were added thereto. The mixturewas irradiated with ultrasonic wave and then recrystallized to obtain6.3 g of an objective white powder at a yield of 67%. A reaction schemeof the above synthesis method is shown in the following (J-3).

Step 2: Synthesis Method of4-phenyl-4′-[4-(9-phenylfluoren-9-yl)phenyl]triphenylamine(abbreviation: BPAFLBi)

3.8 g (8.0 mmol) of 9-(4′-bromo-4-biphenyl)-9-phenylfluorene, 2.0 g (8.0mmol) of 4-phenyl-diphenylamine, 1.0 g (10 mmol) of sodiumtert-butoxide, and 23 mg (0.04 mmol) ofbis(dibenzylideneacetone)palladium(0) were added to a 100-mL three-neckflask, and the atmosphere in the flask was substituted by nitrogen.Then, 20 mL of dehydrated xylene was added to this mixture. After themixture was deaerated while being stirred under reduced pressure, 0.2 mL(0.1 mmol) of tri(tert-butyl)phosphine (10 wt % hexane solution) wasadded thereto. This mixture was heated and stirred under a nitrogenatmosphere at 110° C. for 2 hours to be reacted.

After the reaction, 200 mL of toluene was added to the reaction mixturesolution, and the resulting suspension was filtrated through Florisiland Celite. The obtained filtrate was concentrated and purified bysilica gel column chromatography (developing solvent,toluene:hexane=1:4). The obtained fraction was concentrated, and acetoneand methanol were added thereto. The mixture was irradiated withultrasonic wave and then recrystallized to obtain 4.4 g of an objectivewhite powder at a yield of 86%. A reaction scheme of the above synthesismethod is shown in the following (J-4).

An Rf value of the object by a silica gel thin layer chromatography(TLC) (developing solvent, ethyl acetate:hexane=1:10) was 0.51, that of9-(4′-bromo-4-biphenyl)-9-phenylfluorene was 0.56, and that of4-phenyl-diphenylamine was 0.28.

A compound that was obtained through Step 2 was subjected to a nuclearmagnetic resonance (¹H-NMR) measurement. The measurement data are shownbelow. The ¹H NMR chart is shown in FIGS. 14A and 14B. The measurementresults show that the fluorene derivative BPAFLBi (abbreviation) of thepresent invention, represented by Structural Formula (151) was obtained.

¹H-NMR (CDCl₃, 300 MHz): δ (ppm)=7.04 (t, J=6.6, 1H), 7.12-7.49 (m,30H), 7.55-7.58 (m, 2H), and 7.77 (d, J=7.8, 2H).

A variety of physical properties of BPAFLBi (abbreviation) of theobtained object were measured as described below.

The absorption spectrum (measurement range: 200 nm to 800 nm) wasmeasured using an ultraviolet-visible spectrophotometer (V-550,manufactured by JASCO Corporation). FIG. 15 shows absorption spectra ofa toluene solution and a thin film. The horizontal axis indicates thewavelength (nm) and the vertical axis indicates the absorption intensity(arbitrary unit). The toluene solution put into a quartz cell wasmeasured, and the spectrum in which the absorption spectra of the quartzand toluene were subtracted from the absorption spectrum of the sampleis shown. As the thin film, a sample evaporated on a quartz substratewas measured, and the spectrum in which the absorption spectrum of thequartz was subtracted from the absorption spectrum of the sample isshown. From these spectra, in the case of the toluene solution, anabsorption peak on a long wavelength side was observed at around 340 nm,and in the case of the thin film, an absorption peak on a longwavelength side was observed at around 341 nm.

The emission spectrum was measured using a fluorescencespectrophotometer (FS920, manufactured by Hamamatsu PhotonicsCorporation). FIG. 16 shows emission spectra of a toluene solution and athin film. The horizontal axis indicates the wavelength (nm) and thevertical axis indicates the emission intensity (arbitrary unit). Thetoluene put into a quartz cell was measured, and as the thin film, asample evaporated on a quartz substrate was measured. From thesespectra, in the case of the toluene solution, the maximum emissionwavelength was observed at 386 nm (excitation wavelength: 345 nm), andin the case of the thin film, the maximum emission wavelengths wereobserved at 399, 419 nm (excitation wavelength: 348 nm).

The result of measuring the thin film using a photoelectron spectrometer(AC-2, manufactured by Riken Keiki Co., Ltd.) under the atmosphereindicated that the HOMO level of the thin film was −5.64 eV. The Taucplot of the absorption spectrum of the thin film revealed that theabsorption edge was 3.28 eV. Thus, the energy gap in the solid state wasestimated to be 3.28 eV, which means that the LUMO level of the thinfilm is −2.36 eV. This indicates that BPAFLBi (abbreviation) has arelatively deep HOMO level and a wide band gap (Bg).

The characteristics of oxidation-reduction reaction of BPAFLBi(abbreviation) were examined by a cyclic voltammetry (CV) measurement.Note that an electrochemical analyzer (ALS model 600A or 600C,manufactured by BAS Inc.) was used for the measurement. Since themeasurement method is similar to that of Example 1, the description isomitted.

Note that for the measurement of the oxidation characteristic, thepotential of the working electrode with respect to the referenceelectrode was scanned from −0.10 V to 1.50 V and then from 1.50 V to−0.10 V. As a result, the HOMO level was found to be −5.49 [eV]. Inaddition, the oxidation peak took a similar value even after the 100cycles. Accordingly, it was found that repetition of the oxidationreduction between an oxidation state and a neutral state had favorablecharacteristics.

FIG. 17 shows CV measurement results of the oxidation reactioncharacteristics of BPAFLBi (abbreviation).

The glass transition temperature was measured with a differentialscanning calorimetry (Pyris 1 DSC, manufactured by Perkin Elmer Co.,Ltd.). According to the measurement results, it was found that the glasstransition temperature was 126° C. In this manner, BPAFLBi(abbreviation) had a high glass transition temperature and favorableheat resistance. In addition, the crystallization peak did not exist;thus, it was found that BPAFLBi (abbreviation) was a substance which washard to be crystallized.

Example 3

In Example 3, a method for manufacturing a light-emitting element formedusing 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation:BPAFLP), which is the fluorene derivative synthesized in Example 1 andmeasurement results of element characteristics are described.

The light-emitting element of Example 3 has an element structureillustrated in FIG. 18. Light-Emitting Element 2 is formed using thefluorene derivative (abbreviation: BPAFLP) of the present invention fora hole-transport layer 1512. In addition, Light-Emitting Element 1 whichis a comparative light-emitting element is formed using4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB) forthe hole-transport layer 1512. In order to make the same comparativeconditions between Light-Emitting Element 1 and Light-Emitting Element2, Comparative Light-Emitting Element 1 was formed over the samesubstrate as that of Light-Emitting Element 2, and Light-EmittingElement 1 was compared to Light-Emitting Element 2. Structural Formulaeof an organic compound used in Example 3 are shown below.

First, indium oxide-tin oxide containing silicon oxide was deposited ona substrate 1501 which was a glass substrate by a sputtering method toform a first electrode 1502. Note that the thickness of the firstelectrode 1502 was 110 nm and the electrode area was 2 mm×2 mm.

Next, an EL layer 1503 including a stack of a plurality of layers isformed over the first electrode 1502. In Example 5, the EL layer 1503has a structure in which a first layer 1511 which is a hole-injectionlayer, a second layer 1512 which is a hole-transport layer, a thirdlayer 1513 which is a light-emitting layer, a fourth layer 1514 which isan electron-transport layer, and a fifth layer 1515 which is anelectron-injection layer are sequentially stacked.

The substrate provided with the first electrode 1502 was fixed to asubstrate holder which was provided in a vacuum evaporation apparatus sothat a surface provided with the first electrode 1502 faced downward.The pressure in the vacuum evaporation apparatus was reduced toapproximately 10⁻⁴ Pa. Then, over the first electrode 1502,4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) and molybdenum(VI)oxide were co-evaporated to form the first layer 1511 which is ahole-injection layer. The thickness was 50 nm, and the evaporation ratewas controlled so that the weight ratio of NPB to molybdenum (VI) oxidecould be 4:1=(NPB: molybdenum oxide). Note that the co-evaporationmethod is an evaporation method in which evaporation of a plurality ofmaterials is performed from a plurality of evaporation sources at thesame time in one treatment chamber.

Next, a hole-transport material was deposited on the first layer 1511 toa thickness of 10 nm by an evaporation method using resistance heating,and the second layer 1512 which was a hole-transport layer was formed.Note that Comparative Light-Emitting Element 1 was formed using4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB) andLight-Emitting Element 2 was formed using4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP).

Next, the third layer 1513 which was a light-emitting layer was formedon the second layer 1512 by an evaporation method using resistanceheating. The third layer 1513 was formed by co-evaporating9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPA) and4-(10-phenyl-9-anthryl)-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine(abbreviation: PCBAPA) to a thickness of 30 nm. Here, the evaporationrate was controlled so that the weight ratio of CzPA to PCBAPA could be1:0.10=(CzPA: PCBAPA).

Furthermore, on the third layer 1513, a 10-nm-thick film oftris(8-quinolinolato)aluminum(III) (abbreviation: Alq) and, thereon, a20-nm-thick film of bathophenanthroline (abbreviation: BPhen) wereformed by an evaporation method using resistance heating to form thefourth layer 1514 which was an electron-transport layer.

On the fourth layer 1514, a 1-nm-thick film of lithium fluoride (LiF)was formed as the fifth layer 1515 which was an electron-inject layer.

Lastly, a 200-nm-thick film of aluminum was formed by an evaporationmethod using resistance heating to form the second electrode 1504. Thus,Comparative Light-Emitting Element 1 and Light-Emitting Element 2 wereformed.

Note that Comparative Light-Emitting Element 1 and Light-EmittingElement 2 were formed in the same steps, except for the second layer1512.

Comparative Light-Emitting Element 1 and Light-Emitting Element 2 thusobtained were sealed in a glove box having a nitrogen atmosphere withoutbeing exposed to the air. Then, the operating characteristics thereofwere measured. Note that the measurement was carried out at roomtemperature (in an atmosphere kept at 25° C.).

FIG. 19 shows the current density vs. luminance characteristics ofComparative Light-Emitting Element 1 and Light-Emitting Element 2. FIG.20 shows the voltage vs. luminance characteristics of ComparativeLight-Emitting Element 1 and Light-Emitting Element 2. FIG. 21 shows theluminance vs. current efficiency characteristics of ComparativeLight-Emitting Element 1 and Light-Emitting Element 2. In FIG. 19, thevertical axis represents luminance (cd/m²) and the horizontal axisrepresents current density (mA/cm²). In FIG. 20, the vertical axisrepresents luminance (cd/m²) and the horizontal axis represents voltage(V). In FIG. 21, the vertical axis represents current efficiency (cd/A)and the horizontal axis represents luminance (cd/m²). In addition, Table1 shows the voltage, chromaticity, and current efficiency of each ofComparative Light-Emitting Element 1 and Light-Emitting Element 2 around1000 cd/m².

TABLE 1 Current Voltage efficiency (V) Chromaticity x Chromaticity y(cd/A) Comparative 3.8 0.16 0.19 5.2 Light-Emitting Element 1Light-Emitting 4.2 0.15 0.21 8.5 Element 2

When the drive voltage of Light-Emitting Element 2 was 4.2 V, theluminance and the current value were 880 cd/m² and 0.41 mA,respectively. It was found that in comparison with ComparativeLight-Emitting Element 1 using NPB (abbreviation) for the second layer1512, Light-Emitting Element 2 using BPAFLP (abbreviation) for thesecond layer 1512 has higher current efficiency. This is because thecarrier balance of Light-Emitting Element 2 is considered to be improvedas compared to Light-Emitting Element 1. That is considered that thehole-injection property from the hole-transport layer to thelight-emitting layer was improved because the HOMO level of BPAFLP(abbreviation) was closer to the HOMO level of CzPA (abbreviation) whichis the host material of the light-emitting layer than the HOMO level ofNPB. Further, it is considered that the electron blocking property fromthe light-emitting layer to the hole-transport layer was improvedbecause the LUMO level of BPAFLP (abbreviation) was higher than the LUMOlevel of NPB. Furthermore, it is considered that excitons generated inthe third layer (light-emitting layer) 1513 were not transferred to thesecond layer 1512 which was an adjacent layer (that is to say, notquenched) and were confined because BPAFLP (abbreviation) has a wideband gap (Bg) (in comparison with NPB).

Example 4

In Example 4, a method for manufacturing a light-emitting element formedusing 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation:BPAFLP), which is the fluorene derivative synthesized in Example 1 andmeasurement results of element characteristics are described.

The light-emitting element of Example 4 has an element structureillustrated in FIG. 18. Light-Emitting Element 3 is formed using theabove-described fluorene derivative (abbreviation: BPAFLP) of thepresent invention for a hole-transport layer 1512. Structural Formulaeof an organic compound used in Example 4 are shown below.

First, indium oxide-tin oxide containing silicon oxide was deposited ona substrate 1501 which was a glass substrate by a sputtering method toform a first electrode 1502. Note that the thickness of the firstelectrode 1502 was 110 nm and the electrode area was 2 mm×2 mm.

Next, an EL layer 1503 including a stack of a plurality of layers isformed over the first electrode 1502. In Example 4, the EL layer 1503has a structure in which a first layer 1511 which is a hole-injectionlayer, a second layer 1512 which is a hole-transport layer, a thirdlayer 1513 which is a light-emitting layer, a fourth layer 1514 which isan electron-transport layer, and a fifth layer 1515 which is anelectron-injection layer are sequentially stacked.

The substrate provided with the first electrode 1502 was fixed to asubstrate holder which was provided in a vacuum evaporation apparatus sothat a surface provided with the first electrode 1502 faced downward.The pressure in the vacuum evaporation apparatus was reduced toapproximately 10⁻⁴ Pa. Then, over the first electrode 1502,9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPA) andmolybdenum(VI) oxide were co-evaporated to form the first layer 1511which is a hole-injection layer. The thickness was 50 nm, and theevaporation rate was controlled so that the weight ratio of CzPA tomolybdenum (VI) oxide could be 4:1=(CzPA: molybdenum oxide).

Next, a hole-transport material was deposited on the first layer 1511 toa thickness of 10 nm by an evaporation method using resistance heating,and the second layer 1512 which was a hole-transport layer was formed.Note that Light-Emitting Element 3 was formed using4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP).

Next, the third layer 1513 which was a light-emitting layer was formedon the second layer 1512 by an evaporation method using resistanceheating. The third layer 1513 was formed by co-evaporating9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPA) and4-(10-phenyl-9-anthryl)-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine(abbreviation: PCBAPA) to a thickness of 30 nm. Here, the evaporationrate was controlled so that the weight ratio of CzPA to PCBAPA could be1:0.10=(CzPA: PCBAPA).

After that, in a manner similar to Comparative Light-Emitting Element 1,the fourth layer which was an electron-transport layer, the fifth layerwhich was an electron-injection layer, and a second electrode wereformed. Thus, Light-Emitting Element 3 was formed.

Light-Emitting Element 3 thus obtained was sealed in a glove box havinga nitrogen atmosphere without being exposed to the air. Then, theoperating characteristics of Light-Emitting Element 3 were measured.Note that the measurement was carried out at room temperature (in anatmosphere kept at 25° C.).

FIG. 22 shows the current density vs. luminance characteristics ofLight-Emitting Element 3. FIG. 23 shows the voltage vs. luminancecharacteristics of Light-Emitting Element 3. FIG. 24 shows the luminancevs. current efficiency characteristics of Light-Emitting Element 3. InFIG. 22, the vertical axis represents luminance (cd/m²) and thehorizontal axis represents current density (mA/cm²). In FIG. 23, thevertical axis represents luminance (cd/m²) and the horizontal axisrepresents voltage (V). In FIG. 24, the vertical axis represents currentefficiency (cd/A) and the horizontal axis represents luminance (cd/m²).In addition, Table 2 shows the voltage, chromaticity, and currentefficiency of Light-Emitting Element 3 at around 1000 cd/m².

TABLE 2 Current Voltage efficiency (V) Chromaticity x Chromaticity y(cd/A) Light-Emitting 3.6 0.16 0.22 6.9 Element 3

According to Example 4, it was confirmed that the light-emitting elementusing the fluorene derivative (abbreviation: BPAFLP) of the presentinvention had the characteristics as a light-emitting element and fullyfunctions. Further, from the results of the reliability test, it wasfound that a highly reliable light-emitting element was obtained inwhich a short circuit due to defects of the film or the like is notcaused even if the light-emitting element is made to emit lightcontinuously.

FIG. 25 shows results of a continuous lighting test in whichLight-Emitting Element 3 was continuously lit by constant currentdriving with the initial luminance set at 1000 cd/m² (the vertical axisindicates the relative luminance on the assumption that 1000 cd/m² is100%). From the results of FIG. 25, Light-Emitting Element 3 exhibits78% of the initial luminance even after 1000 hours, which leads to thatLight-Emitting Element 3 has a long lifetime. Therefore, it was foundthat a long-life light-emitting element can be obtained by applicationof BPAFLP (abbreviation) of the present invention.

Example 5

In Example 5, methods for manufacturing a light-emitting element formedusing 4-phenyl-4′-[4-(9-phenylfluoren-9-yl)phenyl]triphenylamine(abbreviation: BPAFLBi) which is the fluorene derivative synthesized inExample 1 and Example 2, and a light-emitting element formed using4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP)and measurement results of element characteristics are described.

The light-emitting elements of Example 5 have an element structureillustrated in FIG. 18. The light-emitting elements are formed using theabove-described fluorene derivative of the present invention for ahole-injection layer and a hole-transport layer. Structural Formulae ofan organic compound used in Example 5 are shown below.

First, indium oxide-tin oxide containing silicon oxide was deposited ona substrate 1501 which was a glass substrate by a sputtering method toform a first electrode 1502. Note that the thickness of the firstelectrode 1502 was 110 nm and the electrode area was 2 mm×2 mm.

Next, an EL layer 1503 including a stack of a plurality of layers isformed over the first electrode 1502. In Example 5, the EL layer 1503has a structure in which a first layer 1511 which is a hole-injectionlayer, a second layer 1512 which is a hole-transport layer, a thirdlayer 1513 which is a light-emitting layer, a fourth layer 1514 which isan electron-transport layer, and a fifth layer 1515 which is anelectron-injection layer are sequentially stacked.

The substrate provided with the first electrode 1502 was fixed to asubstrate holder which was provided in a vacuum evaporation apparatus sothat a surface provided with the first electrode 1502 faced downward.The pressure in the vacuum evaporation apparatus was reduced toapproximately 10⁻⁴ Pa. Then, over the first electrode 1502, the fluorenederivative of an embodiment of the present invention and molybdenum(VI)oxide were co-evaporated to form the first layer 1511 which is ahole-injection layer. The thickness was 50 nm, and the evaporation ratewas controlled so that the weight ratio of the fluorene derivative tomolybdenum (VI) oxide could be 4:1=(the fluorene derivative: molybdenumoxide). Note that Light-Emitting Element 4 is formed using4-phenyl-4′-[4-(9-phenylfluoren-9-yl)phenyl]triphenylamine(abbreviation: BPAFLBi) as the fluorene derivative and Light-EmittingElement 5 is formed using4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP)as the fluorene derivative.

Next, a hole-transport material was deposited on the first layer 1511 toa thickness of 10 nm by an evaporation method using resistance beating,and the second layer 1512 which was a hole-transport layer was formed.Note that Light-Emitting Element 4 was formed using BPAFLBi andLight-Emitting Element 5 was formed using BPAFLP.

Next, the third layer 1513 which was a light-emitting layer was formedon the second layer 1512 by an evaporation method using resistanceheating. Note that in Example 5, the light-emitting layer has two layers(a first light-emitting layer and a second light-emitting layer). Thefirst light-emitting layer was formed over the second layer 1512 byco-evaporating 9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: CzPA) and4-(10-phenyl-9-anthryl)-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine(abbreviation: PCBAPA) to a thickness of 15 nm. Here, the evaporationrate was controlled so that the weight ratio of CzPA to PCBAPA could be1:0.10=(CzPA: PCBAPA).

Next, the second light-emitting layer was formed on the firstlight-emitting layer by an evaporation method using resistance heating.The second layer was formed over the first light-emitting layer byco-evaporating 9-[4-10-phenyl-9-anthryl)phenyl]-9H-carbazole(abbreviation: CzPA) and4-(10-phenyl-9-anthryl)-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine(abbreviation: PCBAPA) to a thickness of 15 nm. Here, the evaporationrate was controlled so that the weight ratio of CzPA to PCBAPA could be1:0.05=(CzPA: PCBAPA).

After that, in a manner similar to Comparative Light-Emitting Element 1,the fourth layer which was an electron-transport layer, the fifth layerwhich was an electron-injection layer, and a second electrode wereformed. Thus, Light-Emitting Element 4 and Light-Emitting Element 5 wereformed.

Note that Light-Emitting Element 4 and Light-Emitting Element 5 wereformed in the same steps, except for the first layer 1511 and the secondlayer 1512.

Light-Emitting Element 4 and Light-Emitting Element 5 thus obtained weresealed in a glove box having a nitrogen atmosphere without being exposedto the air. Then, the operating characteristics thereof were measured.Note that the measurement was carried out at room temperature (in anatmosphere kept at 25° C.).

FIG. 26 shows the current density vs. luminance characteristics ofLight-Emitting Element 4 and Light-Emitting Element 5. FIG. 27 shows thevoltage vs. luminance characteristics of Light-Emitting Element 4 andLight-Emitting Element 5. FIG. 28 shows the luminance vs. currentefficiency characteristics of Light-Emitting Element 4 andLight-Emitting Element 5. In FIG. 26, the vertical axis representsluminance (cd/m²) and the horizontal axis represents current density(mA/cm²). In FIG. 27, the vertical axis represents luminance (cd/m²) andthe horizontal axis represents voltage (V). In FIG. 28, the verticalaxis represents current efficiency (cd/A) and the horizontal axisrepresents luminance (cd/m²). In addition, Table 3 shows the voltage,chromaticity, current efficiency, and external quantum efficiency ofLight-Emitting Element 4 and Light-Emitting Element 5 at around 1000cd/m².

TABLE 3 Current Quantum Voltage Chromaticity Chromaticity efficiencyefficiency (V) x y (cd/A) (%) Light- 3.8 0.16 0.22 7.7 5.0 EmittingElement 4 Light- 4.0 0.16 0.21 7.8 5.2 Emitting Element 5

According to Example 5, it was confirmed that the light-emittingelements each using BPAFLBi (abbreviation) and BPAFLP (abbreviation) hadthe characteristics as a light-emitting element and fully functions.Further, from the results of the reliability test, it was found that ahighly reliable light-emitting element was obtained in which a shortcircuit due to defects of the film or the like was not caused even ifthe light-emitting element was made to emit light continuously.

FIG. 29 shows results of a continuous lighting test in whichLight-Emitting Element 4 and Light-Emitting Element 5 were continuouslylit by constant current driving with the initial luminance set at 1000cd/m² (the vertical axis indicates the relative luminance on theassumption that 1000 cd/m² is 100%). From the results of FIG. 29,Light-Emitting Element 4 exhibits 74% of the initial luminance evenafter 850 hours and Light-Emitting Element 5 exhibits 75% of the initialluminance even after 850 hours, which leads to that Light-EmittingElement 4 and Light-Emitting Element 5 have a long lifetime. Therefore,it was found that a long-life light-emitting element can be obtained byapplication of BPAFLBi (abbreviation) and BPAFLP (abbreviation) of thepresent invention.

Example 6

In Example 6, a method for manufacturing Light-Emitting Element formedusing 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation:BPAFLP), which is the fluorene derivative synthesized in Example 1 andmeasurement results of element characteristics are described.

The light-emitting element of Example 6 has an element structureillustrated in FIG. 18. The light-emitting element 6 is formed using theabove-described fluorene derivative of the present invention for ahole-transport layer. Structural Formulae of an organic compound used inExample 6 are shown below.

First, indium oxide-tin oxide containing silicon oxide was deposited ona substrate 1501 which was a glass substrate by a sputtering method toform a first electrode 1502. Note that the thickness of the firstelectrode 1502 was 110 nm and the electrode area was 2 mm×2 mm.

Next, an EL layer 1503 including a stack of a plurality of layers isformed over the first electrode 1502. In Example 6, the EL layer 1503has a structure in which a first layer 1511 which is a hole-injectionlayer, a second layer 1512 which is a hole-transport layer, a thirdlayer 1513 which is a light-emitting layer, a fourth layer 1514 which isan electron-transport layer, and a fifth layer 1515 which is anelectron-injection layer are sequentially stacked.

The substrate provided with the first electrode 1502 was fixed to asubstrate holder which was provided in a vacuum evaporation apparatus sothat a surface provided with the first electrode 1502 faced downward.The pressure in the vacuum evaporation apparatus was reduced toapproximately 10⁻⁴ Pa. Then, over the first electrode 1502,4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) and molybdenum(VI)oxide were co-evaporated to form the first layer 1511 which was ahole-injection layer. The thickness was 50 nm, and the evaporation ratewas controlled so that the weight ratio of NPB to molybdenum (VI) oxidecould be 4:2=(NPB: molybdenum oxide). Note that the co-evaporationmethod is an evaporation method in which evaporation of a plurality ofmaterials is performed from a plurality of evaporation sources at thesame time in one treatment chamber.

Next, a hole-transport material was deposited on the first layer 1511 toa thickness of 10 nm by an evaporation method using resistance heating,and the second layer 1512 which was a hole-transport layer was formed.Note that Light-Emitting Element 6 was formed using4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP)and Comparative Light-Emitting Element 7 was formed using4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB).

Next, the third layer 1513 which was a light-emitting layer was formedon the second layer 1512 by an evaporation method using resistanceheating. As the third layer 1513,3-phenyl-9-[4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl]-9H-carbazole(abbreviation: CO11II) and (2-phenylpyridinato-N,C^(2′))iridium(III)acetylacetonato (abbreviation: Ir(ppy)₂acac) were co-evaporated to forma 40-nm-thick film. Here, the evaporation rate was controlled so thatthe weight ratio of CO11II to Ir(ppy)₂acac was1:0.08=(CO11II:Ir(ppy)₂acac).

Furthermore, on the third layer 1513, a 10-nm-thick film ofbis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum(III)(abbreviation: BAlq) and, thereon, a 20-nm-thick film ofbathophenanthroline (abbreviation: BPhen) were formed by an evaporationmethod using resistance heating to form the fourth layer 1514 which wasan electron-transport layer.

After that, in a manner similar to Comparative Light-Emitting Element 1,the fourth layer which was an electron-transport layer, the fifth layerwhich was an electron-injection layer, and a second electrode wereformed. Thus, Light-Emitting Element 6 and Comparative Light-EmittingElement 7 were formed.

Note that Light-Emitting Element 6 and Comparative Light-EmittingElement 7 were formed in the same steps, except that of the second layer1512.

Light-Emitting Element 6 and Comparative Light-Emitting Element 7 thusobtained were sealed in a glove box having a nitrogen atmosphere withoutbeing exposed to the air. Then, the operating characteristics thereofwere measured. Note that the measurement was carried out at roomtemperature (in an atmosphere kept at 25° C.).

FIG. 30 shows the current density vs. luminance characteristics ofLight-Emitting Element 6 and Comparative Light-Emitting Element 7. FIG.31 shows the voltage vs. luminance characteristics of Light-EmittingElement 6 and Comparative Light-Emitting Element 7. FIG. 32 shows theluminance vs. current efficiency characteristics of Light-EmittingElement 6 and Comparative Light-Emitting Element 7. In FIG. 30, thevertical axis represents luminance (cd/m²) and the horizontal axisrepresents current density (mA/cm²). In FIG. 31, the vertical axisrepresents luminance (cd/m²) and the horizontal axis represents voltage(V). In FIG. 32, the vertical axis represents current efficiency (cd/A)and the horizontal axis represents luminance (cd/m²). In addition, Table4 shows the voltage, chromaticity, current efficiency, and externalquantum efficiency of Light-Emitting Element 6 and ComparativeLight-Emitting Element 7 at around 1000 cd/m².

TABLE 4 Current Quantum Voltage Chromaticity Chromaticity efficiencyefficiency (V) x y (cd/A) (%) Light- 3.6 0.36 0.61 59 16 EmittingElement 6 Compar- 4.4 0.34 0.57 6.0 1.7 ative Light- Emitting Element 7

FIG. 33 shows emission spectra of Light-Emitting Element 6 andComparative Light-Emitting Element 7.

As shown in FIG. 33, in Comparative Light-Emitting Element 7, anemission wavelength derived from NPB of a hole-transport layer inaddition to an emission wavelength derived from a dopant was observed.This indicates that NPB has low ability to block electrons, wherebyrecombination partly occurs even in NPB which has low internal quantumefficiency. As a result, it is considered that the current efficiencyand external quantum efficiency were decreased. Further, it is thoughtthat since NPB has low triplet excitation energy, triplet excitationenergy is likely to transfer from the light-emitting layer to NPB, whichcauses decrease in the current efficiency and external quantumefficiency. On the other hand, in Light-Emitting Element 6, only anemission derived from a dopant in the light-emitting layer was observedand an emission derived from BPAFLP (abbreviation) in the hole-transportlayer was not observed. Accordingly, it is indicated that BPAFLP hashigh ability to block electrons and also has large triplet excitationenergy. As a result, generated excitation energy was consumed mainly bya dopant which was a phosphorescent material in the light-emitting layerto form light, whereby high current efficiency can be obtained. Thus, itwas confirmed that an element having high efficiency can be obtainedwith use of BPAFLP (abbreviation) of an embodiment of the presentinvention for the hole-transport layer.

Example 7

In Example 7, a method for manufacturing Light-Emitting Element formedeach using 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine(abbreviation: BPAFLP), which is the fluorene derivative synthesized inExample 1 and measurement results of element characteristics isdescribed.

Each of Light-Emitting Element 8 to Light-Emitting Element 10 of Example7 has an element structure illustrated in FIG. 18. Light-EmittingElement 9 was formed using the above-described fluorine derivative ofthe present invention for a transporting layer, and Light-EmittingElement 10 was formed using the above-described fluorine derivative ofthe present invention for a hole-injection layer and a hole-transportlayer, respectively. Structural Formulae of an organic compound used inExample 7 are shown below.

First, indium oxide-tin oxide containing silicon oxide was deposited ona substrate 1501 which was a glass substrate by a sputtering method toform a first electrode 1502. Note that the thickness of the firstelectrode 1502 was 110 nm and the electrode area was 2 mm×2 mm.

Next, an EL layer 1503 including a stack of a plurality of layers isformed over the first electrode 1502. In Example 7, the EL layer 1503has a structure in which a first layer 1511 which is a hole-injectionlayer, a second layer 1512 which is a hole-transport layer, a thirdlayer 1513 which is a light-emitting layer, a fourth layer 1514 which isan electron-transport layer, and a fifth layer 1515 which is anelectron-injection layer are sequentially stacked.

The substrate provided with the first electrode 1502 was fixed to asubstrate holder which was provided in a vacuum evaporation apparatus sothat a surface provided with the first electrode 1502 faced downward.The pressure in the vacuum evaporation apparatus was reduced toapproximately 10⁻⁴ Pa. Then, over the first electrode 1502, ahole-injection material was deposited to a thickness of 50 nm to formthe first layer 1511 which was a hole-injection layer. Note that whenLight-Emitting Element 8 and Light-Emitting Element 9 were formed,4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB) andmolybdenum(VI) oxide were co-evaporated to form the first layer 1511which was a hole-injection layer 1511. The thickness was 50 nm, and theevaporation rate was controlled so that the weight ratio of NPB tomolybdenum (VI) oxide could be 4:2=(NPB: molybdenum oxide). Further,when Light-Emitting Element 10 was formed,4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP)and molybdenum(VI) oxide were co-evaporated to form the first layer 1511which was a hole-injection layer. The thickness was 50 nm, and theevaporation rate was controlled so that the weight ratio of BPAFLP tomolybdenum (VI) oxide could be 4:2=(BPAFLP: molybdenum oxide).

Next, a hole-transport material was deposited on the first layer 1511 toa thickness of 10 nm by an evaporation method using resistance beating,and the second layer 1512 which was a hole-transport layer was formed.Note that Light-Emitting Element 8 was formed using4-phenyl-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation:PCBA1BP)] and Light-Emitting Element 9 and Light-Emitting Element wereformed using 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine(abbreviation: BPAFLP).

Next, the third layer 1513 which was a light-emitting layer was formedon the second layer 1512 by an evaporation method using resistanceheating. As the third layer 1513,3-phenyl-9-[4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl]-9H-carbazole(abbreviation: CO11II),4-phenyl-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation:PCBA1BP), andbis{2-(4-fluorophenyl)-3,5-dimethylpyridinato}(picolinate)iridium(III)(abbreviation: Ir(dmFppr)₂pic) were co-evaporated to form a 40-nm-thickfilm. Here, the evaporation rate was controlled so that the weight ratioof CO11II to PCBA1BP and Ir(dmFppr)₂pic) was1:0.15:0.1=(CO11II:PCBA1BP:Ir(dmFppr)₂pic)).

After that, in a manner similar to Comparative Light-Emitting Element 1,the fourth layer which was an electron-transport layer, the fifth layerwhich was an electron-injection layer, and a second electrode wereformed. Thus, Light-Emitting Element 8 to Light-Emitting Element 10 wereformed.

Note that Light-Emitting Element 8 to Light-Emitting Element 10 wereformed in the same steps, except those of the first layer 1511 and thesecond layer 1512.

Light-Emitting Element 8 to Light-Emitting Element 10 thus obtained weresealed in a glove box having a nitrogen atmosphere without being exposedto the air. Then, the operating characteristics thereof were measured.Note that the measurement was carried out at room temperature (in anatmosphere kept at 25° C.).

FIG. 34 shows the current density vs. luminance characteristics ofLight-Emitting Element 8 to Light-Emitting Element 10. FIG. 35 shows thevoltage vs. luminance characteristics of Light-Emitting Element 8 toLight-Emitting Element 10. FIG. 36 shows the luminance vs. currentefficiency characteristics of Light-Emitting Element 8 to Light-EmittingElement 10. In FIG. 34, the vertical axis represents luminance (cd/m²)and the horizontal axis represents current density (mA/cm²). In FIG. 35,the vertical axis represents luminance (cd/m²) and the horizontal axisrepresents voltage (V). In FIG. 36, the vertical axis represents currentefficiency (cd/A) and the horizontal axis represents luminance (cd/m²).In addition, Table 5 shows the voltage, chromaticity, currentefficiency, and external quantum efficiency of Light-Emitting Element 8to Light-Emitting Element 10 at around 1000 cd/m².

TABLE 5 Current Quantum Voltage Chromaticity Chromaticity efficiencyefficiency (V) x y (cd/A) (%) Light- 4.6 0.41 0.58 61 17 EmittingElement 8 Light- 4.8 0.41 0.58 65 18 Emitting Element 9 Light- 4.6 0.400.58 70 19 Emitting Element 10

High luminous efficiency can be obtained in each of Light-EmittingElement 8 to Light-Emitting Element 10; however, it was found thatLight-Emitting Element 9 using BPAFLP for the hole-transport layer hadhigher current efficiency than Light-Emitting Element 8. Further, it wasfound that Light-Emitting Element 10 using BPAFLP for both thehole-injection layer and the hole-transport layer had higher currentefficiency than Light-Emitting Element 9.

FIG. 37 shows results of a continuous lighting test in whichLight-Emitting Element 8 to Light-Emitting Element 10 were continuouslylit by constant current driving with the initial luminance set at 1000cd/m² (the vertical axis indicates the relative luminance on theassumption that 1000 cd/m² is 100%). From the results of FIG. 37,Light-Emitting Element 8 exhibits 64% of the initial luminance evenafter 650 hours. Light-Emitting Element 9 exhibits 71% of the initialluminance even after 500 hours and Light-Emitting Element 10 exhibits72% of the initial luminance even after 500 hours. Therefore, it wasfound that a long-life light-emitting element can be obtained byapplication of BPAFLP (abbreviation) of an embodiment of the presentinvention.

Example 8

Here, simulation results which indicate the fluorene derivative of anembodiment of the present invention is suitable for a hole-transportmaterial are shown.

Structural Formulae used in the simulation are shown below.

First, the most stable structures of Structural Formula (101)(abbreviation: BPAFLP), Structural Formula (109), Structural Formula(114), Structural Formula (151) (abbreviation: BPAFLBi), StructuralFormula (164), and NPB in the singlet state and the triplet state werecalculated using a density functional theory (TDDFT). Gaussian 03 wasused as a quantum chemistry computational program. As a basis function,6-311G (d, p) was used for H, C, and N atoms. As a functional, B3LYP wasused.

Next, excitation energy of Structural Formula (101) (abbreviation:BPAFLP), Structural Formula (109), Structural Formula (114), StructuralFormula (151) (abbreviation: BPAFLBi), Structural Formula (164), and NPBwas each calculated with use of the most stable structures in thesinglet state and the triplet state which were obtained by the abovecalculation, by time-dependent density functional theory. The basisfunction and functional used for this calculation were the same as thosedescribed above.

Table 6 shows the results of energy levels of the highest occupiedmolecular orbital (HOMO) level of the most stable structures in thesinglet state obtained by the above calculation.

TABLE 6 Structural Structural Formula Structural Structural FormulaStructural (101) Formula Formula (151) Formula Singlet state BPAFLP(109) (114) BPAFLBi (164) NPB Energy −5.13 eV −5.04 eV −5.18 eV −5.13 eV−5.18 eV −4.97 eV levels of HOMO

From the results of Table 6, it was found that the above fluorenederivative had the lower HOMO energy level than NPB. Thus, it was provedthat in the case where any of the above fluorene derivatives was used asa hole-transport material, the fluoren derivatives have excellenthole-injection property into a light-emitting layer having a deeper HOMOlevel in comparison with NPB.

Table 7 shows the results of the first excitation energy (singlet) ofthe most stable structures in the singlet state obtained by calculationusing TDDFT

TABLE 7 The most stable Structural Structural structures FormulaStructural Structural Formula Structural in the (101) Formula Formula(151) Formula singlet state BPAFLP (109) (114) BPAFLBi (164) NPB Thefirst excitation 2.85 eV 2.67 eV 3.01 eV 2.76 eV 2.84 eV 2.50 eV energy(singlet)

From the results of Table 7, it was found that in the case where any ofthe above fluorene derivatives was used as a hole-transport material,the fluorene derivatives hardly released singlet excitons at theboundary between the light-emitting layer and the hole-transport layerto the hole-transport layer side in comparison with NPB.

Table 8 shows the results of the first excitation energy (triplet) ofthe most stable structures in the triplet state obtained by calculationusing TDDFT

TABLE 8 The most stable Structural Structural structures FormulaStructural Structural Formula Structural in the (101) Formula Formula(151) Formula triplet state BPAFLP (109) (114) BPAFLBi (164) NPB Thefirst excitation 1.98 eV 2.03 eV 2.15 eV 1.98 eV 1.98 eV 1.74 eV energy(triplet)

From the results of Table 8, it was found at in a case where any of theabove fluorene derivatives was used as a hole-transport material, thefluorene derivatives hardly released triplet excitons at the boundarybetween the light-emitting layer and the hole-transport layer from thelight-emitting layer to the hole-transport layer side, in comparisonwith NPB. Further, it was found that in a case where any of the fluorenederivatives was used as a phosphorescent host material, a guest materialwas easily excited.

Example 9

In Example 9, a method for manufacturing Light-Emitting Element formedusing 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation:BPAFLP), which is the fluorene derivative synthesized in Example 1 andmeasurement results of element characteristics is described.

An element structure of each of Light-Emitting Element 11 andComparative Light-Emitting Element 12 in Example 9 is illustrated inFIG. 18. Light-Emitting Element 11 was formed using the above-describedfluorene derivative of the present invention for a hole-injection layerand a hole-transport layer.

First, indium oxide-tin oxide containing silicon oxide was deposited ona substrate 1501 which was a glass substrate by a sputtering method toform a first electrode 1502. Note that the thickness of the firstelectrode 1502 was 110 nm and the electrode area was 2 mm×2 mm.

Next, an EL layer 1503 including a stack of a plurality of layers isformed over the first electrode 1502. In Example 9, the EL layer 1503has a structure in which a first layer 1511 which is a hole-injectionlayer, a second layer 1512 which is a hole-transport layer, a thirdlayer 1513 which is a light-emitting layer, a fourth layer 1514 which isan electron-transport layer, and a fifth layer 1515 which is anelectron-injection layer are sequentially stacked.

The substrate provided with the first electrode 1502 was fixed to asubstrate holder which was provided in a vacuum evaporation apparatus sothat a surface provided with the first electrode 1502 faced downward.The pressure in the vacuum evaporation apparatus was reduced toapproximately 10⁻⁴ Pa. Then, over the first electrode 1502, ahole-injection material was deposited to a thickness of 50 nm to formthe first layer 1511 which was a hole-injection layer. WhenLight-Emitting Element 11 was formed,4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP)and molybdenum(VI) oxide were co-evaporated to form the first layer 1511which was a hole-injection layer 1511. The thickness was 50 nm, and theevaporation rate was controlled so that the weight ratio of BPAFLP tomolybdenum (VI) oxide could be 4:2=(BPAFLP: molybdenum oxide). Further,when Comparative Light-Emitting Element 12 was formed,4,4′,4″-tris(carbazol-9-yl)triphenylamine (abbreviation: TCTA) andmolybdenum(VI) oxide were co-evaporated to form the first layer 1511which was a hole-injection layer. The thickness was 50 nm, and theevaporation rate was controlled so that the weight ratio of TCTA tomolybdenum (VI) oxide could be 4:2=(TCTA: molybdenum oxide).

Next, a hole-transport material was deposited on the first layer 1511 toa thickness of 10 nm by an evaporation method using resistance heating,and the second layer 1512 which was a hole-transport layer was formed.Note that Light-Emitting Element 11 was formed using4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP)and Comparative Light-Emitting Element 12 was formed using4,4′,4″-tris(carbazol-9-yl)triphenylamine (abbreviation: TCTA).

Next, the third layer 1513 which was a light-emitting layer was formedon the second layer 1512 by an evaporation method using resistanceheating. As the third layer,9-[4-(4,5-diphenyl-4H-1,2,4-triazol-3-yl)phenyl]-9H-carbazole(abbreviation: CzTAZ1) andbis[2-(4′,6′-difluorophenyl)pyridinato-N,C^(2′)]iridium(I)picolinate(abbreviation: FIrpic) were co-evaporated to form a 30-nm-thick film.Here, the evaporation rate was controlled so that the weight ratio ofCzTAZ1 to FIrpic was 1:0.06=(CzTAZ1: FIrpic).

Furthermore, on the third layer 1513, a 10-nm-thick film of3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole(abbreviated designation: TAZ01) and, thereon, a 20-nm-thick film ofbathopbenanthroline (abbreviation: BPhen) were formed by an evaporationmethod using resistance heating to form the fourth layer 1514 which wasan electron-transport layer.

After that, in a manner similar to Comparative Light-Emitting Element 1,the fifth layer which was an electron-injection layer and a secondelectrode were formed. Thus, Light-Emitting Element 11 and ComparativeLight-Emitting Element 12 were formed.

Note that Light-Emitting Element 11 and Comparative Light-EmittingElement 12 were formed in the same steps, except those of the firstlayer 1511 and the second layer 1512.

Light-Emitting Element 11 and Comparative Light-Emitting Element 12 thusobtained were sealed in a glove box having a nitrogen atmosphere withoutbeing exposed to the air. Then, the operating characteristics thereofwere measured. Note that the measurement was carried out at roomtemperature (in an atmosphere kept at 25° C.).

FIG. 38 shows the current density vs. luminance characteristics ofLight-Emitting Element 11 and Comparative Light-Emitting Element 12.FIG. 39 shows the voltage vs. luminance characteristics ofLight-Emitting Element 11 and Comparative Light-Emitting Element 12.FIG. 40 shows the luminance vs. current efficiency characteristics ofLight-Emitting Element 11 and Comparative Light-Emitting Element 12. InFIG. 38, the vertical axis represents luminance (cd/m²) and thehorizontal axis represents current density (mA/cm²). In FIG. 39, thevertical axis represents luminance (cd/m²) and the horizontal axisrepresents voltage (V). In FIG. 40, the vertical axis represents currentefficiency (cd/A) and the horizontal axis represents luminance (cd/m²).In addition, Table 9 shows the voltage, chromaticity, currentefficiency, and external quantum efficiency of Light-Emitting Element 11and Comparative Light-Emitting Element 12 around 1000 cd/m².

TABLE 9 Volt- Current Quantum age Chromaticity Chromaticity efficiencyefficiency (V) x y (cd/A) (%) Light- 5.2 0.19 0.37 20 9.2 EmittingElement 11 Comparative 5.2 0.19 0.37 18 8.4 Light- Emitting Element 12

When the drive voltage of Light-Emitting Element 11 in which thefluorene derivative BPAFLP (abbreviation) of the present invention wasused for the first layer 1511 and the second layer 1512, was 5.2 V, theluminance was 910 cd/m² and the current value was 0.18 mA. When thedrive voltage of Comparative Light-Emitting Element 12 in which TCTA(abbreviation) was used instead of BPAFLP (abbreviation) was 5.2 V, theluminance was 850 cd/m² and the current value was 0.19 mA. Thus, it wasconfirmed that Light-Emitting Element 11 in which BPAFLP (abbreviation)was used for the first layer 1511 and the second layer 1512 has highercurrent efficiency than Comparative Light-Emitting Element 12. It wasfound that by application of BPAFLP (abbreviation) of an embodiment ofthe present invention to the hole-injection layer and the hole-transportlayer, a light-emitting element with high efficiency can be obtained.

FIG. 41 shows emission spectra of Light-Emitting Element 11 andComparative Light-Emitting Element 12.

In both Light-Emitting Element 11 and Comparative Light-Emitting Element12, an emission spectrum derived from FIrpic (abbreviation) which was aphosphorescent dopant material was observed, and an emission derivedfrom a layer adjacent to the third layer 1513 was not observed. Thisshows that in both of the elements, carriers were preferably recombinedin the third layer 1513, and light could be emitted in favorable carrierbalance. It was indicated that since Light-Emitting Element 11 showedhigher current efficiency than Comparative Light-Emitting Element 12 atthis time, BPAFLP (abbreviation) had more favorable carrier balance(blocked electrons from the third layer 1513 and made more holes flow tothe third layer 1513) and the triplet excitation energy was also high.At this time, the LUMO level of BPAFLP (abbreviation) of an embodimentof the present invention was almost the same as that of TCTA(abbreviation) (−230 eV) and band gap (Bg) of BPAFLP (abbreviation) wasnarrower than that of TCTA (abbreviation) (3.40 eV); therefore, BPAFLP(abbreviation) of an embodiment of the present invention was a materialhaving higher hole-transport property. Accordingly, it was thought thatcarrier recombination can be efficiently performed in the light-emittinglayer, so that higher efficiency can be obtained.

Example 10

In Example 10, a method for manufacturing a light-emitting elementformed using 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine(abbreviation: BPAFLP), which is the fluorene derivative synthesized inExample 1 and measurement results of element characteristics aredescribed.

An element structure of Light-Emitting Element 13 in Example 10 isillustrated in FIG. 18. Light-Emitting Element 13 was formed using theabove-described fluorene derivative (abbreviation: BPAFLP) of thepresent invention for the hole-injection layer and the hole-transportlayer. A structural formula of an organic compound which was used inExample 10 is shown below.

First, indium oxide-tin oxide containing silicon oxide was deposited ona substrate 1501 which was a glass substrate by a sputtering method toform a first electrode 1502. Note that the thickness of the firstelectrode 1502 was 110 nm and the electrode area was 2 mm×2 mm.

Next, an EL layer 1503 including a stack of a plurality of layers isformed over the first electrode 1502. In Example 9, the EL layer 1503has a structure in which a first layer 1511 which is a hole-injectionlayer, a second layer 1512 which is a hole-transport layer, a thirdlayer 1513 which is a light-emitting layer, a fourth layer 1514 which isan electron-transport layer, and a fifth layer 1515 which is anelectron-injection layer are sequentially stacked.

The substrate provided with the first electrode 1502 was fixed to asubstrate holder which was provided in a vacuum evaporation apparatus sothat a surface provided with the first electrode 1502 faced downward.The pressure in the vacuum evaporation apparatus was reduced toapproximately 10⁻⁴ Pa. Then, over the first electrode 1502, ahole-injection material was deposited to a thickness of 50 nm to formthe first layer 1511 which was a hole-injection layer. WhenLight-Emitting Element 13 was formed,4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP)and molybdenum(VI) oxide were co-evaporated to form the first layer 1511which was a hole-injection layer 1511. The thickness was 50 nm, and theevaporation rate was controlled so that the weight ratio of BPAFLP tomolybdenum (VI) oxide could be 4:2=(BPAFLP: molybdenum oxide).

Next, a hole-transport material was deposited on the first layer 1511 toa thickness of 10 nm by an evaporation method using resistance heating,and the second layer 1512 which was a hole-transport layer was formed.Note that Light-Emitting Element 13 was formed using4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP).

Next, the third layer 1513 which was a light-emitting layer was formedon the second layer 1512 by an evaporation method using resistanceheating. As the third layer 1513,4-[3-(triphenylen-2-yl)phenyl]dibenzothiophene (abbreviation:mDBTPTp-II) and tris(2-phenylpyridinato-N,C^(2′))iridium(III)(abbreviation: Ir(ppy)₃) were co-evaporated to form a 40-nm-thick film.Here, the evaporation rate was controlled so that the weight ratio ofmDBTPTp-II to Ir(ppy)₃ was 1:0.08=(mDBTPTp-II: Ir(ppy)₃).

Furthermore, on the third layer 1513, a 10-nm-thick film of mDBTPTp-IIand, thereon, a 20-nm-thick film of bathophenanthroline (abbreviation:BPhen) were formed by an evaporation method using resistance heating toform the fourth layer 1514 which was an electron-transport layer.

After that, in a manner similar to Comparative Light-Emitting Element 1,the fifth layer which was an electron-injection layer and a secondelectrode were formed. Thus, Light-Emitting Element 13 was formed.

Light-Emitting Element 13 thus obtained was sealed in a glove box havinga nitrogen atmosphere without being exposed to the air. Then, theoperating characteristics of Light-Emitting Element 13 were measured.Note that the measurement was carried out at room temperature (in anatmosphere kept at 25° C.).

FIG. 42 shows the current density vs. luminance characteristics ofLight-Emitting Element 13. FIG. 43 shows the voltage vs. luminancecharacteristics of Light-Emitting Element 13. FIG. 44 shows theluminance vs. current efficiency characteristics of Light-EmittingElement 13. In FIG. 42, the vertical axis represents luminance (cd/m²)and the horizontal axis represents current density (mA/cm²). In FIG. 43,the vertical axis represents luminance (cd/m²) and the horizontal axisrepresents voltage (V). In FIG. 44, the vertical axis represents currentefficiency (cd/A) and the horizontal axis represents luminance (cd/m²).In addition, Table 10 shows the voltage, chromaticity, currentefficiency, and external quantum efficiency of Light-Emitting Element 13around 1000 cd/m².

TABLE 10 Current Quantum Voltage Chromaticity Chromaticity efficiencyefficiency (V) x y (cd/A) (%) Light- 4.0 0.33 0.62 67 19 EmittingElement 13

According to Example 10, it was confirmed that the light-emittingelement 13 formed using the fluorene derivative (abbreviation: BPAFLP)of the present invention had sufficient characteristics to function as alight-emitting element. Further, from the results of the reliabilitytest, it was found that a highly reliable light-emitting element wasobtained in which a short circuit due to defects of the film or the likewas not caused even if the light-emitting element was made to emit lightcontinuously.

Furthermore, when a continuous lighting test was conducted in whichLight-Emitting Element 13 was continuously lit by constant currentdriving with the initial luminance set at 1000 cd/m², 86% of the initialluminance was maintained even after 1900 hours. Thus, Light-EmittingElement 13 was found to have a long lifetime. Accordingly, it wasconfirmed that by application of BPAFLP (abbreviation) of an embodimentof the present invention to the hole-injection layer, a light-emittingelement having a long lifetime can be obtained.

Example 11 Synthesis Example 3

In Example 11, a synthesis example of the fluorene derivative which isrepresented as General Formula (G1) in Embodiment 1 and an embodiment ofthe present invention is described. Specifically, a synthesis method of4-phenyl-3′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation:mBPAFLP), which is shown in Structural Formula (118) in Embodiment 1, isdescribed. A structure of mBPAFLP is shown below.

Step 1: Synthesis Method of 9-(3-bromophenyl)-9-phenylfluorene

In a 200-mL three-neck flask, 30 mL of a dehydrated THF solution of 4.2g (18 mmol) of 2-bromobiphenyl was added thereto, and then the mixturesolution was stirred at −78° C. 11 mL (18 mmol) of an n-BuLi hexanesolution (1.57 M) was dropped into this mixture solution, and themixture was stirred for 2.5 hours. After that, 40 mL of dehydrated THFsolution of 3.9 g (15 mmol) of 3-bromobenzophenone was dropped to thismixture, and the mixture was stirred for 2 hours and at room temperaturefor 16 hours.

After the reaction, 1N-diluted hydrochloric acid was added to thismixture solution, and the mixture was stirred for 1 hour. This mixturewas washed with water. The obtained organic phase was concentrated toobtain a candy-like substance.

Then, in a 200-mL recovery flask, this candy-like substance, 20 mL ofglacial acetic acid, and 1.0 mL of hydrochloric acid were put, and themixture was heated and stirred under a nitrogen atmosphere at 130° C.for 2 hours to be reacted.

After the reaction, this reaction mixture solution was dropped into 150mL of ice-cooled water, so that a caramel-like solid was precipitated.An insoluble component of this was removed by decantation. Thiscaramel-like solid was dissolved in 100 mL of toluene, and a saturatedsodium hydrogen carbonate aqueous solution was added thereto withstirring the toluene solution until no more bubble comes out. An organiclayer of this was washed with water, and then silica gel was added toadsorb moisture. The filtrate which was obtained by filtration of themixture was concentrated, and methanol was added thereto. The mixturewas irradiated with ultrasonic wave while being cooled with ice and thenthe produced solid was filtrated. 4.9 g of an objective white powder wasobtained at a yield of 83%. A reaction scheme of the above synthesismethod is shown in the following (J-5).

Step 2: Synthesis Method of4-phenyl-3′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: mBPAFLP)

2.4 g (6.0 mmol) of 9-(3-bromophenyl)-9-phenylfluorene, 1.5 g (6.0 mmol)of 4-phenyl-diphenylamine, 1.0 g (10 mmol) of sodium tert-butoxide, and3.0 mg (0.005 mmol) of bis(dibenzylideneacetone)palladium(0) were addedto a 200-mL three-neck flask, and the atmosphere in the flask wassubstituted by nitrogen. Then, 25 mL of dehydrated xylene was added tothis mixture. After the mixture was deaerated while being stirred underreduced pressure, 0.2 mL (0.1 mmol) of tri(tert-butyl)phosphine (10 wt %hexane solution) was added thereto. This mixture was heated and stirredunder a nitrogen atmosphere at 130° C. for 2.5 hours to be reacted.

After the reaction, 200 mL of toluene was added to the reaction mixturesolution, and the resulting suspension was filtrated through Florisil(produced by Wako Pure Chemical Industries, Ltd., Catalog No.540-00135), alumina, and Celite (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 531-16855). The obtained filtrate wasconcentrated and purified by silica gel column chromatography(developing solvent, toluene:hexane=1:4). The obtained fraction wasconcentrated, and acetone and methanol were added thereto. The mixturewas irradiated with supersonic and then recrystallized to obtain 3.2 gof an objective white powder at a yield of 97%. A reaction scheme of theabove synthesis method is shown in the following (J-6).

An Rf value of the object by a silica gel thin layer chromatography(TLC) (developing solvent, ethyl acetate:hexane=1:10) was 0.51, that of9-(3-bromophenyl)-9-phenylfluorene was 0.62, and that of4-phenyl-diphenylamine was 0.39.

A compound that was obtained through Step 2 was subjected to a nuclearmagnetic resonance (¹H-NMR) measurement. The measurement data are shownbelow. The ¹H-NMR chart is shown in FIGS. 45A and 45B. The measurementresults show that the fluorene derivative mBPAFLP (abbreviation) of thepresent invention, represented by Structural Formula (118) was obtained.

¹H-NMR (CDCl₃, 300 MHz): δ (ppm)=6.72 (d, J=8.4, 1H), 6.92-736 (m, 22H),7.40-7.44 (m, 4H), 7.54-7.57 (m, 2H), and 7.72-7.75 (m, 2H).

Molecular weight of the compound obtained in Step 2 was measured by aGC-MS detector (ITQ1100 ion trap GCMS system, manufactured by ThermoFisher). Accordingly, a main peak with a molecular weight of 561.3 (modeis EI+) was detected, and it was confirmed that an objective mBPAFLP(abbreviation) was obtained.

A variety of physical properties of mBPAFLP (abbreviation) of theobtained object were measured as described below.

The absorption spectrum (measurement range: 200 nm to 800 nm) wasmeasured using an ultraviolet-visible spectrophotometer (V-550,manufactured by JASCO Corporation). FIG. 46 shows absorption spectra ofa toluene solution and a thin film. The horizontal axis indicates thewavelength (nm) and the vertical axis indicates the absorption intensity(arbitrary unit). The toluene solution put into a quartz cell wasmeasured. The spectrum in which the absorption spectra of the quartz andtoluene were subtracted from the absorption spectrum of the sample isshown. Samples in which a thin film was evaporated on a quartz substratewere measured, and the spectrum in which the absorption spectrum of thequartz was subtracted from the absorption spectrum of the sample isshown. From these spectra, in the case of the toluene solution,absorption peaks on a long wavelength side were observed at around 310nm and 325 nm, and in the case of the thin film, absorption peaks on along wavelength side were observed at around 312 nm and 329 nm.

The emission spectrum was measured using a fluorescencespectrophotometer (FS920, manufactured by Hamamatsu PhotonicsCorporation). FIG. 47 shows emission spectra of a toluene solution and athin film. The horizontal axis indicates the wavelength (nm) and thevertical axis indicates the emission intensity (arbitrary unit). Thetoluene solution put into a quartz cell was measured, and as the thinfilm, a sample evaporated on a quartz substrate was measured. From thesespectra, in the case of the toluene solution, the maximum emissionwavelength was observed at 382 nm (excitation wavelength: 340 nm), andin the case of the thin film, the maximum emission wavelengths wasobserved at 393 nm (excitation wavelength: 343 nm).

The result of measuring the thin film using a photoelectron spectrometer(AC-2, manufactured by Riken Keiki Co., Ltd.) under the atmosphereindicated that the HOMO level of the thin film was −5.73 eV. The Taucplot of the absorption spectrum of the thin film revealed that theabsorption edge was 334 eV. Thus, the energy gap in the solid state wasestimated to be 3.34 eV, which means that the LUMO level of the thinfilm is −2.39 eV. This indicates that mBPAFLP (abbreviation) has arelatively deep HOMO level and a wide band gap (Bg).

The characteristics of oxidation-reduction reaction of mBPAFLP(abbreviation) were examined by a cyclic voltammetry (CV) measurement.Note that an electrochemical analyzer (ALS model 600A or 600C,manufactured by BAS Inc.) was used for the measurement.

Note that for the measurement of the oxidation reaction characteristic,the potential of the working electrode with respect to the referenceelectrode was scanned from −0.38 V to 0.69 V and then from 0.69 V to0.38 V. As a result, the HOMO level was found to be −5.53 [eV]. Inaddition, the oxidation peak took a similar value even after the 100cycles. Accordingly, it was found that repetition of the oxidationreduction between an oxidation state and a neutral state had favorablecharacteristics.

A melting point was measured. The melting point was 211° C. to 212° C.

Example 12

In Example 12, a method for manufacturing a light-emitting elementformed using 4-phenyl-3′-(9-phenylfluoren-9-yl)triphenylamine(abbreviation: mBPAFLP), which is the fluorene derivative synthesized inExample 1 and measurement results of element characteristics aredescribed.

An element structure of a light-emitting element in Example 12 isillustrated in FIG. 18. Light-Emitting Element 14 was formed using theabove-described fluorene derivative (abbreviation: mBPAFLP) of anembodiment of the present invention for a hole-injection layer and ahole-transport layer.

First, indium oxide-tin oxide containing silicon oxide was deposited ona substrate 1501 which was a glass substrate by a sputtering method toform a first electrode 1502. Note that the thickness of the firstelectrode 1502 was 110 nm and the electrode area was 2 mm×2 mm.

Next, an EL layer 1503 including a stack of a plurality of layers isformed over the first electrode 1502. In Example 9, the EL layer 1503has a structure in which a first layer 1511 which is a hole-injectionlayer, a second layer 1512 which is a hole-transport layer, a thirdlayer 1513 which is a light-emitting layer, a fourth layer 1514 which isan electron-transport layer, and a fifth layer 1515 which is anelectron-injection layer are sequentially stacked.

The substrate provided with the first electrode 1502 was fixed to asubstrate holder which was provided in a vacuum evaporation apparatus sothat a surface provided with the first electrode 1502 faced downward.The pressure in the vacuum evaporation apparatus was reduced toapproximately 10⁻⁴ Pa. Then, over the first electrode 1502, ahole-injection material was deposited to a thickness of 50 nm to formthe first layer 1511 which was a hole-injection layer. WhenLight-Emitting Element 14 was formed,4-phenyl-3′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: mBPAFLP)and molybdenum(VI) oxide were co-evaporated to form the first layer 1511which was a hole-injection layer 1511. The thickness was 50 nm, and theevaporation rate was controlled so that the weight ratio of mBPAFLP(abbreviation) to molybdenum (VI) oxide could be 4:2=(mBPAFLP:molybdenum oxide). Further, when Comparative Light-Emitting Element 15was formed, 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl(abbreviation: NPB) and molybdenum(VI) oxide were co-evaporated to formthe first layer 1511 which was a hole-injection layer. The thickness was50 nm, and the evaporation rate was controlled so that the weight ratioof NPB to molybdenum (VI) oxide could be 4:2=(NPB: molybdenum oxide).

Next, a hole-transport material was deposited on the first layer 1511 toa thickness of 10 nm by an evaporation method using resistance heating,and the second layer 1512 which was a hole-transport layer was formed.Note that Light-Emitting Element 14 was formed using4-phenyl-3′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: mBPAFLP)and Comparative Light-Emitting Element 15 was formed using4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB).

Next, the third layer 1513 which was a light-emitting layer was formedon the second layer 1512 by an evaporation method using resistanceheating. As the third layer 1513,9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPA) and4-(10-phenyl-9-anthryl)-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine(abbreviation: PCBAPA) were co-evaporated to form a 30-nm-thick film.Here, the evaporation rate was controlled so that the weight ratio ofCzPA to PCBAPA was 1:0.075=(CzPA: PCBAPA).

Furthermore, on the third layer 1513, a 10-nm-thick film oftris(8-quinolinolato)aluminum(III) (abbreviation: Alq) and, thereon, a20-nm-thick film of bathophenanthroline (abbreviation: BPhen) wereformed by an evaporation method using resistance heating to form thefourth layer 1514 which was an electron-transport layer.

On the fourth layer 1514, a 1-nm-thick film of lithium fluoride (LiF)was formed as the fifth layer 1515 which was an electron-injectionlayer.

Finally, a film of aluminum was formed to have a thickness of 200 nm byan evaporation method using resistance heating, whereby a secondelectrode 1504 was formed. In this manner, Light-Emitting Element 14 andComparative Light-Emitting Element 15 were formed.

Note that Light-Emitting Element 14 and Comparative Light-EmittingElement were formed in the same steps, except those of the first layer1511 and the second layer 1512.

Light-Emitting Element 14 and Comparative Light-Emitting Element 15 thusobtained were sealed in a glove box having a nitrogen atmosphere withoutbeing exposed to the air. Then, the operating characteristics thereofwere measured. Note that the measurement was carried out at roomtemperature (in an atmosphere kept at 25° C.).

FIG. 48 shows the current density vs. luminance characteristics ofLight-Emitting Element 14 and Comparative Light-Emitting Element 15.FIG. 49 shows the voltage vs. luminance characteristics ofLight-Emitting Element 14 and Comparative Light-Emitting Element 15.FIG. 50 shows the luminance vs. current efficiency characteristics ofLight-Emitting Element 14 and Comparative Light-Emitting Element 15. InFIG. 48, the vertical axis represents luminance (cd/m²) and thehorizontal axis represents current density (mA/cm²). In FIG. 49, thevertical axis represents luminance (cd/m²) and the horizontal axisrepresents voltage (V). In FIG. 50, the vertical axis represents currentefficiency (cd/A) and the horizontal axis represents luminance (cd/m²).In addition, Table 11 shows the voltage, chromaticity, and currentefficiency of Light-Emitting Element 14 and Comparative Light-EmittingElement 15 around 1000 cd/m².

TABLE 11 Current Voltage efficiency (V) Chromaticity x Chromaticity y(cd/A) Light-Emitting 3.50 0.16 0.20 3.63 Element 14 Comparative 3.400.16 0.22 6.01 Light-Emitting Element 15

When the drive voltage of Light-Emitting Element 14 was 3.4 V, theluminance was 1100 cd/m² and the current value was 0.72 mA. It was foundthat Light-Emitting Element 14 using mBPAFLP (abbreviation) for thesecond layer 1512 had higher current efficiency than ComparativeLight-Emitting Element 15 using NPB for the second layer 1512. It wasunderstood that this was because carrier balance of Light-EmittingElement 14 was improved as compared with Comparative Light-EmittingElement 15. It was thought that since the HOMO level of mBPAFLP(abbreviation) was close to the HOMO level of CzPA (abbreviation) whichwas a host material of the light-emitting layer (in comparison withNPB), the hole-injection property of mBPAFLP (abbreviation), from thehole-transport layer to the light-emitting layer, was improved. Further,it was thought that since mBPAFLP (abbreviation) had a high LUMO level(in comparison with NPB), the electron-blocking property of mBPAFLP(abbreviation), from the light-emitting layer to the hole-transportlayer, was improved. Furthermore, it was thought that since mBPAFLP(abbreviation) had a wide band gap (Bg) (in comparison with NPB),excitons generated in the third layer (light-emitting layer) 1513 werenot transferred to the second layer 1512 which was an adjacent layer(that is to say, not quenched) and were confined.

In addition, when a continuous lighting test was conducted in whichLight-Emitting Element 14 and Comparative Light-Emitting Element 15 werecontinuously lit by constant current driving with the initial luminanceset at 1000 cd/m², after 280 hours, Light-Emitting Element 14 exhibits80% of the initial luminance and Comparative Light-Emitting Element 15exhibits 72% of the initial luminance, which leads to thatLight-Emitting Element 14 and Comparative Light-Emitting Element 15 havea long lifetime. Thus, it was found that by application of mBPAFLP(abbreviation) of the present invention, a light-emitting element havinga long lifetime can be obtained.

(Reference Example 1)

A synthesis method of4-(10-phenyl-9-anthryl-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine(abbreviation: PCBAPA) which is used in Example 3 to Example 5 isdescribed in detail.

The synthesis scheme of4-(10-phenyl-9-anthryl)-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine(abbreviation: PCBAPA) is shown in the following (X-1).

7.8 g (12 mmol) of 9-4-bromophenyl)-10-phenylanthracene, 4.8 g (12 mmol)of 4-(9-phenyl-9H-carbazol-3-yl)diphenylamine (abbreviation: PCBA), and5.2 g (52 mmol) of sodium tert-butoxide were added to a 300-mLthree-neck flask, and the atmosphere in the flask was substituted bynitrogen. Then, 60 mL of toluene and 0.30 mL of tri(tert-butyl)phosphine(10 wt % hexane solution) were added to this mixture. After the mixturewas deaerated while being stirred under reduced pressure, 136 mg (0.24mmol) of bis(dibenzylideneacetone)palladium(0) was added thereto. Thismixture was stirred at 100° C. for 3 hours. After the stirring, about 50mL of toluene was added to this mixture. The mixture was subjected tosuction filtration through Celite (produced by Wako Pure Chemicalindustries, Ltd., Catalog No. 531-16855), alumina, and Florisil(produced by Wako Pure Chemical Industries, Ltd., Catalog No.540-00135). The obtained filtrate was concentrated to give a yellowsolid. This solid was recrystallized with toluene/hexane to give 6.6 gof a light yellow powdered solid PCBAPA, which was the object of thesynthesis, at a yield of 75%.

Then, 3.0 g of the obtained light yellow powdered solid was sublimatedand purified by a train sublimation method. For sublimation purificationconditions, PCBAPA was heated at 350° C. under a pressure of 8.7 Pa witha flow rate of argon gas of 3.0 mL/min. After the sublimationpurification, 2.7 g of a light yellow solid of PCBAPA was obtained at ayield of 90%.

The obtained compound was subjected to a nuclear magnetic resonance(¹H-NMR) measurement. The measurement data are shown below.

¹H-NMR (CDCl₃, 300 MHz): δ (ppm)=7.09-7.14 (m, 1H), 7.28-7.72 (m, 33H),7.88 (d, J=8.4 Hz, 2H), 8.19 (d, J=7.2 Hz, 1H), and 8.37 (d, J=1.5 Hz,1H).

The measurement results show that4-(10-phenyl-9-anthryl)-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine(abbreviation: PCBAPA) was obtained.

Light-Emitting Element 1 to Light-Emitting Element 5 described in theabove examples can be formed with use of4-(10-phenyl-9-anthryl)-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine(abbreviation: PCBAPA).

(Reference Example 2)

A synthesis method of3-phenyl-9-[4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl]-9H-carbazole(abbreviation: CO11II) which is used in Example 6 and Example 7 isdescribed in detail.

The synthesis scheme of3-phenyl-9-[4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl]-9H-carbazole(abbreviation: CO11II) is shown in (Y-1).

2.3 g (6.6 mmol) of 2-(4-iodophenyl)-5-phenyl-1,3,4-oxadiazole, 1.6 g(6.6 mmol) of 3-phenyl-9H-carbazole, and 1.4 g (15 mmol) of sodiumtert-butoxide were added to a 100 mL three-necked flask, and theatmosphere in the flask was replaced with nitrogen. To this mixture wereadded 30 mL of toluene and 02 mL of a 10 wt % hexane solution oftri(tert-butyl)phosphine, and the mixture was degassed by reducing thepressure of the flask with an aspirator, and then, the atmosphere in theflask was replaced with nitrogen. To the mixture was added 0.058 g (0.10mmol) of bis(dibenzylideneacetone)palladium(0), followed by stirringunder a nitrogen stream at 80° C. for 15 hours. After the stirring,toluene was added to the mixture, and this suspension was washed with asaturated sodium carbonate aqueous solution and saturated saline in thisorder. Then, magnesium sulfate was added to the organic layer to adsorbmoisture. After that, suction filtration was performed on this mixtureto obtain filtrate. Suction filtration was performed with Cellite (WakoPure Chemical Industries. Ltd., catalog number: 540-16855) on theobtained filtrate, and thus a filtrate was obtained. A compound obtainedby concentrating the obtained filtrate was purified by silica gel columnchromatography. The column chromatography was performed first usingtoluene as a developing solvent and then using a mixed solvent oftoluene:ethyl acetate=4:1 as a developing solvent. Acetone was added toa solid obtained by concentrating the obtained fraction, and washed withultrasonic wave irradiation. This mixture was subjected to suctionfiltration to collect a solid. The collected solid was recrystallizedwith a mixed solvent of chloroform and hexane, so that 2.0 g of a powderwhite solid was obtained at a yield of 64%.

1.1 g of the obtained white solid was sublimated and purified by a trainsublimation method. The sublimation purification was carried out underreduced pressure of 3.0 Pa, with a flow rate of argon at 5 mL/min, at240° C. for 16 hours. Thus, 0.98 g of the white solid was obtained at ayield of 89%.

The obtained compound was subjected to a nuclear magnetic resonance(¹H-NMR) measurement. The measurement data are shown below.

¹H-NMR (CDCl₃, 300 MHz): δ (ppm)=7.30-7.76 (m, 13H), 7.79 (d, J=8.3 Hz,2H), 8.14-8.24 (m, 3H), 8.35 (sd, J=1.5 Hz, 1H), and 8.39 (d, J=8.8 Hz,2H).

The measurement results show that3-phenyl-9-[4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl]-9H-carbazole(abbreviation: CO11II) was obtained.

Light-Emitting Element 6 to Light-Emitting Element 10 described in theabove examples can be formed with use of3-phenyl-9-[4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl]-9H-carbazole(abbreviation: CO11II).

(Reference Example 3)

A synthesis method of4-phenyl-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation:PCBA1BP) which is used in Example 7 is described in detail.

The synthesis scheme of4-phenyl-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation:PCBA1BP) is shown in (Z-1).

In a 100-mL three-neck flask, 2.0 g (4.9 mmol) of4-(9-phenyl-9H-carbazol-3-yl)diphenylamine, 1.1 g (4.9 mmol) of4-bromobiphenyl, and 2.0 g (20 mmol) of sodium tert-butoxide were put,and the atmosphere in the flask was substituted by nitrogen. Then, 50 mLof toluene and 0.30 mL of tri(tert-butyl)phosphine (10 wt % hexanesolution) were added to this mixture.

After the mixture was deaerated while being stirred under reducedpressure, 0.10 g of bis(dibenzylideneacetone)palladium(0) was addedthereto. This mixture was heated and stirred at 80° C. for 5 hours to bereacted. After the reaction, toluene was added to this reaction mixture.This suspension was subjected to suction filtration through Celite(produced by Wako Pure Chemical Industries, Ltd., Catalog No.531-16855), alumina, and Florisil (produced by Wako Pure ChemicalIndustries, Ltd., Catalog No. 540-00135), and thus a filtrate wasobtained. The obtained filtrate was washed with a saturated sodiumcarbonate aqueous solution and saturated saline in this order. Then,magnesium sulfate was added to the organic layer to adsorb moisture.After the drying, suction filtration was performed on the mixture toremove the magnesium sulfate, and thus a filtrate was obtained.

The obtained filtrate was concentrated, and purified by silica gelcolumn chromatography. The silica gel column chromatography wasperformed by, first, using a mixture solvent of toluene:hexane=1:9 as adeveloping solvent, and then using a mixture solvent oftoluene:hexane=3:7 as another developing solvent. A solid which wasobtained by concentrating the obtained fraction was recrystallized witha mixture solvent of chloroform and hexane to obtain 2.3 g of a whitepowder-like solid at a yield of 84%.

1.2 g of the obtained white solid was sublimated and purified by a trainsublimation method. The sublimation purification was carried out underreduced pressure of 7.0 Pa, with a flow rate of argon at 3 mL/min, at280° C. for 20 hours. Thus, 1.1 g of the white solid was obtained at ayield of 89%.

The obtained compound was subjected to a nuclear magnetic resonance(¹H-NMR) measurement. The measurement data are shown below.

¹H-NMR (DMSO-d₆, 300 MHz): δ (ppm)=7.05-7.20 (m, 7H), 7.28-7.78 (m,21H), 8.34 (d, J=7.8 Hz, 1H), and 8.57 (s, 1H).

The measurement results show that4-phenyl-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation:PCBA1BP) was obtained.

Light-Emitting Element 8 to Light-Emitting Element 10 described in theabove examples can be formed with use of4-phenyl-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation:PCBA1BP).

(Reference Example 4)

Another synthesis method of4-phenyl-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation:PCBA1BP) which is different from the method described in ReferenceExample 3 is described in detail. This synthesis method is preferablebecause an object with higher purity can be easily obtained with highyield.

Step 1: Synthesis Method of 3-(4-bromophenyl)-9-phenyl-9H-carbazole

A synthesis scheme of 3-(4-bromophenyl)-9-phenyl-9H-carbazole is shownin (Z-2).

In a 300-mL three-neck flask, a mixture of 14 g (50 mmol) of4-bromoiodobenzene, 14 g (50 mmol) of 9-phenyl-9H-carbazol-3-boronicacid, 110 mg (0.5 mmol) of palladium(II) acetate, 300 mg (1.0 mmol) oftri(o-tolyl)phosphine, 50 mL of toluene, 10 mL of ethanol, and 25 mL ofa potassium carbonate aqueous solution (2 mol/L) was deaerated whilebeing stirred under reduced pressure and was heated and stirred under anitrogen atmosphere at 80° C. for 6 hours to be reacted.

After the reaction, 200 mL of toluene was added to the reaction mixturesolution, and the resulting suspension was filtrated through Florisil(produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135)and Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No.531-16855). The obtained filtrate was washed with water, and magnesiumsulfate was added thereto to adsorb moisture. This suspension wasfiltrated to obtain a filtrate. The obtained filtrate was concentratedand purified by silica gel column chromatography. At this time, a mixedsolvent of toluene and hexane (toluene:hexane=1:4) was used as adeveloping solvent for the chromatography. The obtained fraction wasconcentrated, and hexane was added thereto. The mixture was irradiatedwith ultrasonic wave and then recrystallized, so that 15 g of anobjective white powder was obtained at a yield of 75%.

An Rf value of the object by a silica gel thin layer chromatography(TLC) (developing solvent, ethyl acetate:hexane=1:10) was 0.32 and thatof 4-bromoiodobenzene was 0.74.

Further, an RF value of 1,4-bis(9-phenyl-9H-carbazol-3-yl)benzene, whichwas a by-product, (developing solvent, ethyl acetate:hexane=1:10) was0.23; however, spots were slightly observed on TLC in this reactionsuspension. As a result, it was understood that since part of iodine hadhigher reactivity than part of bromo in 4-bromoiodobenzene which was adihalide and was used for the source material, it was selectively(preferentially) reacted with 9-phenyl-9H-carbazol-3-boronic acid whichwas a boron compound (that is, the dihalide and the boron compound wasreacted almost at 1:1). Furthermore, since the RF value of the object issufficiently far from the RF value of the by-product, the object and theby-product can be easily separated in the above-describedchromatography.

The obtained compound in Step 1 was subjected to a nuclear magneticresonance (¹H-NMR) measurement. The measurement data are shown below.

¹H-NMR (CDCl₃, 300 MHz): δ (ppm)=7.24-7.32 (m, 1H), 7.40-7.64 (m, 13H),8.17 (d, J=7.2, 1H), and 8.29 (s, 1H).

The measurement results show that3-(4-bromophenyl)-9-phenyl-9H-carbazole, which was the object, wasobtained.

Molecular weight of the above compound was measured by a GC-MS detector(ITQ1100 ion trap GC/MS system, manufactured by Thermo Fisher ScientificK.K.). Accordingly, a main peak with molecular weight of 397.13 (mode isEI+) was detected, and it was confirmed that3-(4-bromophenyl)-9-phenyl-9H-carbazole, which was the object, wasobtained.

A peak derived from 1,4-bis(9-phenyl-9H-carbazol-3-yl)benzene (molecularweight, 560.2), which was a by-product, was not detected by this GC-MSdetector. Thus, it was confirmed that by the reaction in Step 1, anobject with higher purity can be easily obtained with extremely highyield.

Step 2: Synthesis Method of 4-phenyl-4′-(9phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBA1BP)

A synthesis scheme of4-phenyl-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation:PCBA1BP) is shown in (Z-3).

4-phenyl-diphenylamine and 3-(4-bromophenyl)-9-phenyl-9H-carbazole wereheated and stirred in an organic solvent using a palladium catalyst, aligand of the palladium catalyst, and a base to be reacted.

After the reaction, this reaction mixture solution was purified toobtain an objective white powder.

The obtained compound was subjected to a nuclear magnetic resonance(¹H-NMR) measurement. From the measurement results, as in ReferenceExample 3, it was confirmed that4-phenyl-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation:PCBA1BP), which is an object, can be obtained.

As described above, it was confirmed that by the synthesis methoddescribed in Reference Example 4, an object with higher purity can beeasily obtained with extremely high yield.

This application is based on Japanese Patent Application Serial No.2009-131504 filed with Japan Patent Office on May 29, 2009, the entirecontents of which are hereby incorporated by reference.

The invention claimed is:
 1. A synthesis method of a fluorene derivativecomprising: coupling a first compound and a second compound, wherein thefirst compound is a Formula (a3):

wherein: R¹ to R⁸ are independently any one of a hydrogen atom, an alkylgroup having 1 to 6 carbon atoms, a substituted or unsubstituted phenylgroup, and a substituted or unsubstituted biphenyl group; α³ is asubstituted or unsubstituted arylene group having 6 to 12 carbon atoms;α⁴ is a substituted or unsubstituted 1,3-phenylene group; Ar⁴ is any oneof an alkyl group having 1 to 6 carbon atoms, and a substituted orunsubstituted aryl group having 6 to 12 carbon atoms; and X² is halogen;and J is 1, and k is 0 or 1, wherein the second compound is a formula(a6),

wherein: Ar¹ and Ar² are independently any of an aryl group having 6 to13 carbon atoms in a ring, α¹ and α² are independently a substituted orunsubstituted arylene group having 6 to 12 carbon atoms; and m and n areindependently 0 or
 1. 2. The synthesis method according to claim 1,wherein R¹ to R⁸ are independently any one of Formulae (R-1) to (R-9):


3. The synthesis method according to claim 1, wherein α¹ to α⁴ areindependently any one of Formulae (α-1) to (α-3):


4. The synthesis method according to claim 1, wherein Ar⁴ is any ofFormulae (Ar3-1) to (Ar3-8):


5. The synthesis method according to claim 1, wherein X² is any ofbromine and iodine.
 6. The synthesis method according to claim 1,wherein the first compound is Formula:


7. The synthesis method according to claim 1, wherein Ar⁴ is asubstituted aryl group having 6 to 12 carbon atoms, and the substitutedaryl group comprises one or more of the following substituents: a methylgroup, an ethyl group, a propyl group, a pentyl group, a hexyl group, aphenyl group and a biphenyl group.